JP2021121675A - Liquid composition, and method for producing film and layered body using the liquid composition - Google Patents

Abstract

To provide a liquid composition whereby a resin powder can be uniformly dispersed in a resin or the like without being scattered and a method for producing the same, and a method for producing a film, a laminate or the like by using the liquid composition.SOLUTION: A liquid composition comprises a liquid medium and a resin powder dispersed in the liquid medium. The resin powder has a volume-based cumulative 90% diameter of 8 μm or less. The resin powder is a resin containing a specific polymer (X), including powder of polytetrafluoroethylene or inorganic filler. There is also provided a method for producing the liquid composition. There is further provided a method for producing a film, a laminate or the like by using the liquid composition.SELECTED DRAWING: None

Description

The present invention relates to a liquid composition and a method for producing a film and a laminate using the liquid composition.

In recent years, the demand for various printed circuit boards has been increasing along with the weight reduction, miniaturization, and high density of electronic products. As the printed circuit board, for example, a printed circuit board in which a metal foil is laminated on a substrate made of an insulating material such as polyimide and the metal foil is patterned to form a circuit is used. Printed circuit boards are required to have excellent electrical characteristics (low dielectric constant, etc.) corresponding to frequencies in a high frequency band, and excellent heat resistance that can withstand solder reflow.

As a material having a low dielectric constant and useful for a printed circuit board, a film containing a resin composition composed of polytetrafluoroethylene and having a fluoropolymer fine powder having an average particle size of 0.02 to 5 μm filled in polyimide has been proposed. (Patent Document 1). In the production of the film, a fluoropolymer fine powder is mixed with a polyamic acid solution to form a liquid composition, the liquid composition is applied onto a flat surface, dried, and then the polyamic acid is imidized by heating.

Further, as useful materials for the printed substrate, a resin powder having an average particle size of 0.02 to 50 μm containing a fluorine-containing copolymer having a functional group such as a carbonyl group-containing group, and a cured product of a thermosetting resin are used. A laminate in which a layer containing the above is formed on a metal foil has also been proposed (Patent Document 2). In the production of the laminate, the resin powder is dispersed in a solution containing a thermosetting resin to obtain a liquid composition, the liquid composition is applied to the surface of a metal foil or the like, dried, and then cured.

Japanese Unexamined Patent Publication No. 2005-142572 International Publication No. 2016/017801

In each of the production methods of Patent Documents 1 and 2, a fluoropolymer fine powder before being mixed with a polyamic acid solution and a resin powder before being mixed with a solution containing a thermosetting resin are treated as powder. However, when these are treated as powders, the powders are likely to scatter and adhere to the wall surface of the container when they are put into a mixing container or reaction container, and they are likely to become lumps when mixed with other liquids and are uniformly dispersed. It is difficult to make it. In the mass production process, it is important that these powders can be made into a dispersion liquid in advance and put into a mixing vessel or a reaction vessel through a piping line.

An object of the present invention is to provide a liquid composition in which a resin powder is dispersed in a liquid medium. Another object of the present invention is to provide a method for producing a film or a laminate using the liquid composition.

The present invention has the following configurations.
[1] A liquid medium and a resin powder dispersed in the liquid medium are contained, the average particle size of the resin powder is 0.3 to 6 μm, the volume-based cumulative 90% diameter is 8 μm or less, and the resin powder is the following polymer ( A liquid composition characterized by being a resin containing X).
Polymer (X): A fluoropolymer having a unit based on tetrafluoroethylene, which contains at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group. Fluoropolymer.
[2] The liquid composition of [1], wherein the polymer (X) is a fluorine-containing copolymer having a unit based on tetrafluoroethylene and a unit having the functional group.
[3] The liquid composition of [1] or [2], wherein the polymer (X) is a fluorine-containing copolymer further having a unit based on perfluoro (alkyl vinyl ether).
[4] The liquid composition according to any one of [1] to [3], wherein the liquid composition further contains a surfactant.
[5] The liquid composition according to any one of [1] to [3], wherein the liquid composition further contains a resin powder composed of a polymer other than the polymer (X) or an inorganic filler.

[6] The following fluorine-containing copolymer is contained in an amount of 80% by mass or more based on the total amount of the film, and the thermal expansion (shrinkage) change ratio (x direction (large thermal expansion (shrinkage) rate) and y direction (small thermal expansion (shrinkage)). A film having a ratio of rate) x / y) of 1.0 to 1.3.
Fluorine-containing copolymer: A fluorine-containing copolymer having a unit based on tetrafluoroethylene and a unit having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group. ..
[7] The film of [6], wherein the number of optically non-uniform objects of 20 μm or more is 20 or less in an area of ^{10 cm 2.}
[8] The film of [6] or [7], wherein the arithmetic average roughness Ra of the surface of the film is 2.0 μm or more.

[9] A laminate characterized by having a base material and a layer made of any of the films [6] to [8] on one side or both sides of the base material.
[10] The laminate of [9], wherein the base material is a metal base material and the thickness of the film layer is 15 μm or less.
[11] The laminate of [9] or [10] having a warpage rate of 25% or less.
[12] An interlayer insulating film, a solder resist or a coverlay film having a layer made of the film of the above [6].

[13] A method for producing a film, which comprises forming a film of the liquid composition according to any one of the above [1] to [5] and removing the liquid medium.
[14] The production method of [13], wherein the reinforcing fiber base material is impregnated to form a film.
[15] The production method according to [13] or [14], wherein the film has a relative permittivity of 2.0 to 3.5.

[16] The liquid composition according to any one of [1] to [5] is formed into a film on a base material, and the liquid medium is removed to form a resin layer laminated on the base material. A method for manufacturing a laminated body.
[17] The production method according to [16], wherein the arithmetic average roughness Ra of the exposed surface of the resin layer is 2.0 μm or more.
[18] The method for producing [16] or [17], wherein after removing the liquid medium, heating is performed while injecting thermal radiation and an inert gas radiated from a heating plate that emits far infrared rays toward one surface. ..
[19] The production method according to any one of [16] to [18], wherein the resin layer is formed and then the surface of the resin layer is plasma-treated.
[20] The production method according to any one of [16] to [19], wherein the resin layer has a relative permittivity of 2.0 to 3.5.
[21] The production method according to any one of [16] to [20], wherein the base material is a metal base material.

[22] A laminate having a resin layer on at least one side is produced by the production method according to any one of [16] to [21], and then the obtained laminate is used as a second base material with the surface of the resin layer as the laminate surface. A method for manufacturing a laminated body, which comprises laminating with.
[23] The second base material is a prepreg, and the matrix resin of the prepreg is a thermoplastic resin having a melting point of 280 ° C. or lower or a thermosetting resin having a thermosetting temperature of 280 ° C. or lower, at 120 to 300 ° C. The manufacturing method of [22], which is heat-pressed and laminated.
[24] A printed circuit board characterized by etching the metal layer of a laminate having a metal layer on at least one side produced by the production method according to any one of [16] to [23] to form a pattern. Manufacturing method.

By using the liquid composition of the present invention, the resin powder can be uniformly dispersed in the resin, its raw material, or the like without scattering the resin powder. Further, according to the production method of the present invention using the above liquid composition, a film or a laminate in which defects due to non-uniform dispersion of the resin powder are suppressed can be obtained.

The meanings of the following terms in the present specification are as follows.
The "relative permittivity" is a value measured by the SPDR (Spirit Post Dielectric Resonator) method at a frequency of 2.5 GHz under an environment within the range of 23 ° C ± 2 ° C and 50 ± 5% RH. ..
The "unit" in a polymer means an atomic group derived from one molecule of the monomer formed by polymerizing the monomer. The unit may be an atomic group directly formed by a polymerization reaction, or an atomic group in which a part of the atomic group is converted into another structure by treating the polymer obtained by the polymerization reaction. May be good.
"(Meta) acrylate" is a general term for acrylate and methacrylate.
"Arithmetic Mean Roughness (Ra)" is an arithmetic mean roughness measured based on JIS B0601: 2013 (ISO4287: 1997, Amd.1: 2009). The reference length rl (cutoff value λc) for the roughness curve when calculating Ra was set to 0.8 mm.

[Liquid composition]
The liquid composition of the present invention is a liquid composition containing a liquid medium and a resin powder dispersed in the liquid medium, and the resin powder contains a polymer (X) described later. In addition, the average particle size of the fat powder of the tree is 0.3 to 6 μm, and the volume-based cumulative 90% diameter (D90) is 8 μm or less.
The liquid medium, which is a dispersion medium, is an inert component that is liquid at room temperature, and is composed of an inorganic solvent such as water, an organic solvent, or the like. The liquid medium preferably has a lower boiling point than other components contained in the liquid composition and can be volatilized and removed by heating or the like.
The resin powder may contain a polymer other than the polymer (X).
Further, the liquid composition may have components other than the liquid medium and the resin powder. For example, a component that improves dispersion stability such as a surfactant, a filler composed of inorganic particles, non-meltable organic particles, or the like, a resin powder different from the resin in the above resin powder, or a curable or non-curable solution dissolved in a liquid medium. Examples include sex resins.
As other components contained in the liquid composition of the present invention, surfactants and fillers are particularly preferable.

The polymer (X) is a fluorine-containing polymer containing a unit (hereinafter referred to as “TFE unit”) based on tetrafluoroethylene (hereinafter referred to as “TFE”), and is a carbonyl group-containing group or a hydroxy group. , A fluoropolymer having at least one functional group (hereinafter, also referred to as “functional group (i)”) selected from the group consisting of an epoxy group and an isocyanate group.
The functional group (i) may be contained in the unit in the polymer (X), in which case the unit having the functional group (i) may be a unit having a fluorine atom and having a fluorine atom. It may be a unit that does not. Hereinafter, the unit having the functional group (i) is also referred to as "unit (1)". The unit (1) is preferably a unit having no fluorine atom.
Further, the functional group (i) may be contained in the terminal group of the main chain of the polymer (X), in which case the polymer (X) may have a unit (1) and has. It does not have to be. The terminal group having a functional group (i) is a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and has a functional group (i), or the functional group (i) is used in the reaction of polymer formation. By using the resulting polymerization initiator or chain transfer agent, a terminal group having a functional group (i) is formed. Further, the functional group (i) can be introduced into the terminal group after the polymer is formed. As the functional group (i) contained in the terminal group, an alkoxycarbonyl group, a carbonate group, a carboxy group, a fluoroformyl group, an acid anhydride residue, and a hydroxy group are preferable.

As the polymer (X), a copolymer having a unit (1) and a TFE unit is preferable. Further, in that case, the polymer (X) may further have a unit other than the unit (1) and the TFE unit, if necessary. As the unit other than the unit (1) and the TFE unit, a perfluoro unit such as a PAVE unit or an HFP unit described later is preferable.
Hereinafter, the present invention will be described by taking a polymer (X), which is a copolymer having a unit (1) and a TFE unit, as an example.

The carbonyl group-containing group in the functional group (i) is not particularly limited as long as it is a group containing a carbonyl group in the structure. For example, a group having a carbonyl group between carbon atoms of a hydrocarbon group and a carbonate group. , Carboxy group, haloformyl group, alkoxycarbonyl group, acid anhydride residue, polyfluoroalkoxycarbonyl group, fatty acid residue and the like. Among them, a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group and an acid from the viewpoint of improving mechanical grindability and fusion with metal. Anhydrous residues are preferred, and carboxy groups and acid anhydride residues are more preferred.

Examples of the hydrocarbon group in the group having a carbonyl group between the carbon atoms of the hydrocarbon group include an alkylene group having 2 to 8 carbon atoms. The number of carbon atoms of the alkylene group is the number of carbon atoms in the portion of the alkylene group other than the carbonyl group. The alkylene group may be linear or branched.
The haloformyl group is a group represented by -C (= O) -X (where X is a halogen atom). Examples of the halogen atom in the haloformyl group include a fluorine atom and a chlorine atom, and a fluorine atom is preferable. That is, as the haloformyl group, a fluoroformyl group (also referred to as a carbonylfluoride group) is preferable.
The alkoxy group in the alkoxycarbonyl group may be linear or branched. As the alkoxy group, an alkoxy group having 1 to 8 carbon atoms is preferable, and a methoxy group or an ethoxy group is particularly preferable.

As the unit (1), a unit based on a monomer having a functional group (i) (hereinafter, also referred to as “monomer (m1)”) is preferable. The monomer (m1) may have one or more functional groups (i). When the monomer (m1) has two or more functional groups (i), the functional groups (i) may be the same or different.
As the monomer (m1), a compound having one functional group (i) and one polymerizable double bond is preferable.
As the monomer (m1), one type may be used alone, or two or more types may be used in combination.

Among the monomers (m1), examples of the monomer having a carbonyl group-containing group include a cyclic hydrocarbon compound having an acid anhydride residue and a polymerizable unsaturated bond (hereinafter, “monomer (m11)”. ) ”, Monomer having a carboxy group (hereinafter, also referred to as“ monomer (m12) ”), vinyl ester, (meth) acrylate, CF ₂ = CFOR ^{f1 COOX 1} (where R ^f1 is , A perfluoroalkylene group having 1 to 10 carbon atoms which may contain an etheric oxygen atom, and X ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

Examples of the monomer (m11) include acid anhydrides of unsaturated dicarboxylic acids. Examples of the acid anhydride of the unsaturated dicarboxylic acid include itaconic anhydride (hereinafter, also referred to as “IAH”), citraconic anhydride (hereinafter, also referred to as “CAH”), and 5-norbornene-2,3-dicarboxylic acid. Examples thereof include acid anhydride (also known as hymic anhydride; hereinafter also referred to as “NAH”) and maleic anhydride.
Examples of the monomer (m12) include unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid and maleic acid, and unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid. Can be mentioned.
Examples of the vinyl ester include vinyl acetate, chloroacetic acid vinyl, vinyl butanoate, vinyl pivalate, vinyl benzoate and the like.
Examples of the (meth) acrylate include (polyfluoroalkyl) acrylate and (polyfluoroalkyl) methacrylate.

Examples of the monomer containing a hydroxy group include vinyl esters, vinyl ethers, allyl ethers, unsaturated carboxylic acid esters ((meth) acrylate, crotonic acid ester, etc.), one at the end or side chain. Examples thereof include compounds having the above hydroxy groups and unsaturated alcohols. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl crotonic acid, allyl alcohol and the like.
Examples of the monomer containing an epoxy group include unsaturated glycidyl ethers (for example, allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, etc.), unsaturated glycidyl esters (for example, glycidyl acrylate, etc.). Glycidyl methacrylate, etc.) and the like.
Examples of the monomer containing an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, and 1,1-bis ((meth) acryloyloxymethyl). Ethyl isocyanate and the like can be mentioned.

The unit (1) preferably has at least a carbonyl group-containing group as the functional group (i) from the viewpoint of improving the mechanical greasability and the fusion property with the metal. As the monomer (m1), a monomer having a carbonyl group-containing group is preferable.
As the monomer having a carbonyl group-containing group, a monomer (m11) is preferable from the viewpoint of improving thermal stability and fusion with a metal. Of these, IAH, CAH and NAH are particularly preferred. When at least one selected from the group consisting of IAH, CAH and NAH is used, an acid is used without using a special polymerization method (see JP-A-11-193312) required when maleic anhydride is used. A fluorine-containing copolymer containing an anhydride residue can be easily produced. Among IAH, CAH and NAH, NAH is preferable because it has better adhesion.

The polymer (X) has a unit (hereinafter, referred to as "PAVE unit") based on perfluoro (alkyl vinyl ether) (hereinafter, also referred to as "PAVE") as a unit other than the unit (1) and the TFE unit. You may.

Examples of the PAVE include CF ₂ = CFOR ^f2 (where R ^f2 is a perfluoroalkyl group having 1 to 10 carbon atoms which may contain an ethereal oxygen atom). The perfluoroalkyl group in R ^f2 may be linear or branched. The ^{number of carbon atoms of R f2} is preferably 1 to 3.
The ^{_{CF 2 = CFOR f2, CF 2}} = CFOCF 3, CF 2 = CFOCF 2 CF 3, CF 2 = CFOCF 2 CF 2 CF 3 ( hereinafter also referred to as _{"PPVE".), CF 2 = CFOCF 2} CF 2 CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F and the like can be mentioned, and PPVE is preferable.
One type of PAVE may be used alone, or two or more types may be used in combination.

The polymer (X) may have a unit based on hexafluoropropylene (hereinafter, also referred to as “HFP”) (hereinafter, referred to as “HFP unit”) as a unit other than the unit (1) and the TFE unit. good.

The polymer (X) may have a unit other than the PAVE unit and the HFP unit (hereinafter, referred to as “another unit”) as a unit other than the unit (1) and the TFE unit.

As other units, a unit based on a fluorine-containing monomer (however, the monomer (m1), TFE, PAVE and HFP are excluded), and a non-fluorine-containing monomer (however, the monomer (m1)) are used. Excludes).

As the fluorine-containing monomer, a fluorine-containing compound having one polymerizable double bond is preferable, and for example, fluoroolefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, and chlorotrifluoroethylene (however, TFE). And HFP are excluded.), CF ₂ = CFOR ^f3 SO ₂ X ³ (However, R ^f3 is a perfluoroalkylene group having 1 to 10 carbon atoms or a perfluoroalkylene having 2 to 10 carbon atoms including an ether oxygen atom. Group, X ³ is a halogen atom or a hydroxy group), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ (where p is 1 or 2), CH ₂ = CX ⁴ (CF) ₂ ) _q X ⁵ (where X ⁴ is a hydrogen atom or a fluorine atom, q is an integer of 2 to 10 and X ⁵ is a hydrogen atom or a fluorine atom), perfluoro (2-methylene-4-). Methyl-1,3-dioxolane) and the like. These may be used alone or in combination of two or more.
As the fluorine-containing monomer, vinylidene fluoride, chlorotrifluoroethylene and CH ₂ = CX ⁴ (CF ₂ ) _q X ⁵ are preferable.
CH ₂ = CX ⁴ (CF ₂ ) _q X ⁵ includes CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ = CF (CF ₂ ) ₃ H, CH ₂ = CF (CF ₂ ) ₄ H and the like, and CH ₂ = CH (CF ₂ ) ₄ F or CH ₂ = CH (CF ₂ ) ₂ F is preferable.

As the non-fluorine-containing monomer, a non-fluorine-containing compound having one polymerizable double bond is preferable, and examples thereof include olefins having 3 or less carbon atoms such as ethylene and propylene. These may be used alone or in combination of two or more.
As the monomer (m42), ethylene or propylene is preferable, and ethylene is particularly preferable.

The fluorine-containing monomer and the non-fluorine-containing monomer may be used alone or in combination of two or more. Further, the fluorine-containing monomer and the non-fluorine-containing monomer may be used in combination.

As the polymer (X), the polymer (X-1) and the polymer (X-2) described later are preferable, and the polymer (X-1) is particularly preferable.

The polymer (X-1) has a unit (1), a TFE unit, and a PAVE unit, and the ratio of the unit (1) to the total of all the units is 0.01 to 3 mol%, and the ratio of the TFE unit. Is 90 to 99.89 mol%, and the ratio of PAVE units is 0.1 to 9.99 mol%.

The polymer (X-1) may further have at least one of the HFP unit and the other unit, if desired. The polymer (X-1) may be composed of a unit (1), a TFE unit and a PAVE unit, or may be composed of a unit (1), a TFE unit, a PAVE unit and an HFP unit, and the unit (1). It may be composed of a TFE unit, a PAVE unit and another unit, or may be composed of a unit (1), a TFE unit, a PAVE unit, an HFP unit and another unit.

As the polymer (X-1), a copolymer having a unit based on a monomer containing a carbonyl group-containing group, a TFE unit and a PAVE unit is preferable, and a unit based on the monomer (m11) and a TFE unit are used. Copolymers with PAVE units are particularly preferred. Specific examples of the preferred polymer (X-1) include TFE / PPVE / NAH copolymers, TFE / PPVE / IAH copolymers, TFE / PPVE / CAH copolymers and the like.

The polymer (X-1) may have a functional group (i) as a terminal group. The functional group (i) can be introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent, or the like used in the production of the polymer (X-1).

The ratio of the unit (1) to the total of all the units constituting the polymer (X-1) is 0.01 to 3 mol%, preferably 0.03 to 2 mol%, and 0.05 to 1 mol%. Is particularly preferable. When the content of the unit (1) is at least the lower limit of the above range, a resin powder having a large bulk density can be easily obtained. In addition, the interlayer adhesion between the film or the like formed by the liquid composition and another material (metal or the like) is excellent. When the content of the unit (1) is not more than the upper limit of the above range, the heat resistance and color of the polymer (X-1) are good.

The ratio of TFE units to the total of all the units constituting the polymer (X-1) is 90 to 99.89 mol%, preferably 95 to 99.47 mol%, and particularly 96 to 98.95 mol%. preferable. When the content of TFE units is equal to or higher than the lower limit of the above range, the polymer (X-1) is excellent in electrical characteristics (low dielectric constant, etc.), heat resistance, chemical resistance, and the like. When the content of TFE units is not more than the upper limit of the above range, the polymer (X-1) is excellent in melt moldability, stress crack resistance and the like.

The ratio of PAVE units to the total of all the units constituting the polymer (X-1) is 0.1 to 9.99 mol%, preferably 0.5 to 9.97 mol%, and 1 to 9.95. Mol% is particularly preferred. When the content of PAVE units is within the above range, the polymer (X-1) is excellent in moldability.

The ratio of the total of units (1), TFE units and PAVE units to the total of all units in the polymer (X-1) is preferably 90 mol% or more, more preferably 95 mol% or more, and 98 mol% or more. Is even more preferable. The upper limit of the ratio is not particularly limited and may be 100 mol%.

The content of each unit in the polymer (X-1) can be measured by NMR analysis such as molten nuclear magnetic resonance (NMR) analysis, fluorine content analysis, infrared absorption spectrum analysis and the like. For example, as described in JP-A-2007-314720, the ratio (mol%) of the unit (1) to all the units constituting the polymer (X-1) by using a method such as infrared absorption spectrum analysis. ) Can be obtained.

The polymer (X-2) has a unit (1), a TFE unit, and an HFP unit, and the ratio of the unit (1) to the total of all units is 0.01 to 3 mol%, and the ratio of the TFE unit. Is 90 to 99.89 mol%, and the proportion of HFP units is 0.1 to 9.99 mol% (excluding the polymer (X-1)).

The polymer (X-2) may further have PAVE units and other units, if desired. The polymer (X-2) may consist of a unit (1), a unit (2), and an HFP unit, or may consist of a unit (1), a TFE unit, an HFP unit, and a PAVE unit (however, the polymer). (X-1) may be excluded.), It may be composed of a unit (1), a TFE unit, an HFP unit and another unit, and the unit (1), a TFE unit, an HFP unit, a PAVE unit and another unit may be used. (However, the polymer (X-1) is excluded).

As the polymer (X-2), a copolymer having a unit based on a monomer containing a carbonyl group-containing group, a TFE unit and an HFP unit is preferable, and a unit based on the monomer (m11) and a TFE unit are used. Copolymers with HFP units are particularly preferred. Specific examples of the preferred polymer (X-2) include TFE / HFP / NAH copolymers, TFE / HFP / IAH copolymers, TFE / HFP / CAH copolymers, and the like.
The polymer (X-2) may have a terminal group having a functional group (i), similarly to the polymer (X-1).

The ratio of the unit (1) to the total of all the units constituting the polymer (X-2) is 0.01 to 3 mol%, preferably 0.02 to 2 mol%, and 0.05 to 1.5. Mol% is particularly preferred. When the content of the unit (1) is at least the lower limit of the above range, a resin powder having a large bulk density can be easily obtained. In addition, the interlayer adhesion between the film or the like formed by the liquid composition and another material (metal or the like) is excellent. When the content of the unit (1) is not more than the upper limit of the above range, the heat resistance and color of the polymer (X-2) are good.

The ratio of TFE units to the total of all the units constituting the polymer (X-2) is 90 to 99.89 mol%, preferably 91 to 98 mol%, and particularly preferably 92 to 96 mol%. When the content of TFE units is equal to or higher than the lower limit of the above range, the polymer (X-2) is excellent in electrical characteristics (low dielectric constant, etc.), heat resistance, chemical resistance, and the like. When the content of TFE units is not more than the upper limit of the above range, the polymer (X-2) is excellent in melt moldability, stress crack resistance and the like.

The ratio of HFP units to the total of all the units constituting the polymer (X-2) is 0.1 to 9.99 mol%, preferably 1 to 9 mol%, and particularly preferably 2 to 8 mol%. When the content of HFP units is within the above range, the polymer (X-2) is excellent in moldability.

The ratio of the total of units (1), TFE units, and HFP units to the total of all units in the polymer (X-2) is preferably 90 mol% or more, more preferably 95 mol% or more, and 98 mol% or more. Is even more preferable. The upper limit of the ratio is not particularly limited and may be 100 mol%.

The melting point of the polymer (X) is preferably 260 to 380 ° C. When the melting point of the polymer (X) is 260 ° C. or higher, the heat resistance is excellent. When the melting point of the polymer (X) is 380 ° C. or lower, the moldability is excellent. In particular, problems such as surface unevenness due to particles after molding are unlikely to occur.
Further, it is preferable that the polymer (X) can be melt-molded. In addition, "melt moldable" means to show melt fluidity. "Exhibiting melt fluidity" means that there is a temperature at which the melt flow rate is 0.1 to 1000 g / 10 minutes at a temperature 20 ° C. or higher higher than the melting point of the resin under the condition of a load of 49 N. .. "Melting flow rate" means the melt mass flow rate (MFR) defined in JIS K 7210: 1999 (ISO 1133: 1997). The melting point of the melt-moldable polymer (X) is more preferably 260 to 320 ° C., further preferably 280 to 320 ° C., particularly preferably 295 to 315 ° C., and most preferably 295 to 310 ° C. When the melting point of the polymer (X) is at least the lower limit of the above range, the heat resistance is excellent. When the melting point of the polymer (X) is not more than the upper limit of the above range, the melt moldability is excellent.
The melting point of the polymer (X) can be adjusted by the type and content ratio of the units constituting the polymer (X), the molecular weight, and the like. For example, the higher the proportion of TFE units, the higher the melting point tends to be.

The MFR of the polymer (X) is preferably 0.1 to 1000 g / 10 minutes, more preferably 0.5 to 100 g / 10 minutes, further preferably 1 to 30 g / 10 minutes, and particularly preferably 5 to 20 g / 10 minutes. preferable. When the MFR is not more than the lower limit of the above range, the polymer (X) is excellent in molding processability, and the surface smoothness and appearance of a film or the like formed by using the liquid composition are excellent. When the MFR is not more than the upper limit of the above range, the polymer (X) is excellent in mechanical strength, and the film or the like formed by using the liquid composition is excellent in mechanical strength.

The MFR is a measure of the molecular weight of the polymer (X), and a large MFR indicates a small molecular weight, and a small MFR indicates a large molecular weight. The molecular weight of the polymer (X), and thus the MFR, can be adjusted according to the production conditions of the polymer (X). For example, if the polymerization time is shortened during the polymerization of the monomer, the MFR tends to increase.

The relative permittivity of the polymer (X) is preferably 2.5 or less, more preferably 2.4 or less, and particularly preferably 2.0 to 2.4. The lower the relative permittivity of the polymer (X), the better the electrical characteristics of the film formed by using the liquid composition. For example, when the film is used as a substrate of a printed circuit board, excellent transmission efficiency can be obtained. ..
The relative permittivity of the copolymer (X) can be adjusted by the content of TFE units.

The polymer (X) can be produced by a conventional method. Examples of the method for producing the polymer (X) include the methods described in [0053] to [0060] of International Publication No. 2016/017801.

The resin powder may contain a polymer other than the polymer (X).
The polymer other than the polymer (X) that may be contained in the resin powder is not particularly limited as long as the characteristics of electrical reliability are not impaired. For example, a fluoropolymer other than the polymer (X), Examples include aromatic polyester, polyamide-imide, and thermoplastic polyimide. As the polymer, a fluorine-containing polymer other than the polymer (X) is preferable from the viewpoint of electrical reliability. The polymer may be used alone or in combination of two or more.
Examples of the fluorine-containing copolymer other than the polymer (X) include polytetrafluoroethylene (hereinafter, also referred to as “PTFE”) and a TFE / PAVE copolymer (however, the polymer (X) is excluded). , TFE / HFP copolymer (excluding polymer (X)), ethylene / TFE copolymer and the like. As the fluorine-containing polymer other than the polymer (X), those having a melting point of 280 ° C. or higher are preferable from the viewpoint of heat resistance.

The resin powder preferably contains the polymer (X) as a main component. If the polymer (X) is the main component, a resin powder having a high bulk density can be easily obtained. The larger the bulk density of the resin powder, the better the handleability. The phrase "the resin powder contains the polymer (X) as a main component" means that the ratio of the polymer (X) to the total amount of the resin powder is 80% by mass or more. The ratio of the polymer (X) to the total amount of the powder material is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

The average particle size of the resin powder is 0.3 to 6 μm, preferably 0.4 to 5 μm, more preferably 0.5 to 4.5 μm, further preferably 0.7 to 4 μm, and 1 to 3.5 μm. Especially preferable. When the average particle size of the resin powder is equal to or higher than the lower limit of the above range, the fluidity of the resin powder is sufficient, the handling is easy, and the average particle size is small. Therefore, the thermoplastic resin or the like is filled with the resin powder. The rate can be increased. The higher the filling rate, the better the electrical characteristics (low dielectric constant, etc.) of the film or the like formed by using the liquid composition. Further, the smaller the average particle size of the resin powder, the thinner the thickness of the film formed by using the liquid composition can be made, and it is easy to make the thickness useful for, for example, a flexible printed circuit board. When the average particle size of the resin powder is not more than the upper limit of the above range, the dispersibility of the resin powder in the liquid medium is excellent.

The average particle size of the resin powder is a volume-based cumulative 50% diameter (D50) determined by the laser diffraction / scattering method. That is, the particle size distribution is measured by a laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population as 100%, and the particle size is the point at which the cumulative volume is 50% on the cumulative curve.

The volume-based cumulative 90% diameter (D90) of the resin powder is 8 μm or less, preferably 6 μm or less, and particularly preferably 1.5 to 5 μm. When D90 is not more than the upper limit value, the dispersibility of the resin powder in the liquid medium is excellent.
The resin powder D90 is obtained by a laser diffraction / scattering method. That is, the particle size distribution is measured by a laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population as 100%, and the particle size is the point at which the cumulative volume is 90% on the cumulative curve.

The sparse filling bulk density of the resin powder is preferably 0.05 g / mL or more, more preferably 0.05 to 0.5 g / mL, and particularly preferably 0.08 to 0.5 g / mL.
The densely packed bulk density of the resin powder is preferably 0.05 g / mL or more, more preferably 0.05 to 0.8 g / mL, and particularly preferably 0.1 to 0.8 g / mL.
The larger the sparsely filled bulk density or the densely packed bulk density, the better the handleability of the resin powder. In addition, the filling rate of the resin powder in the thermoplastic resin or the like can be increased. If the sparsely packed bulk density or the densely packed bulk density is equal to or less than the upper limit of the above range, it can be used in a general-purpose process.

As a method for producing a resin powder, a polymer (X) obtained by polymerization or a powder material containing a commercially available polymer (X) is pulverized as necessary and then classified (sieving, etc.) to have an average particle size. A method of obtaining a resin powder having a thickness of 0.3 to 6 μm and a D90 of 8 μm or less can be mentioned. When the polymer (X) is produced by solution polymerization, suspension polymerization or emulsion polymerization, the organic solvent or aqueous medium used for the polymerization is removed to recover the granular polymer (X), and then pulverization or classification ( Sieving, etc.). When the average particle size of the polymer (X) obtained by the polymerization is 0.3 to 6 μm and the D90 is 8 μm or less, the polymer (X) can be used as it is as a resin powder.
When the resin powder contains a polymer other than the polymer (X), it is preferable that the polymer and the polymer (X) are melt-kneaded and then pulverized for classification.

As the method for pulverizing and classifying the powder material, the methods described in [0065] to [0069] of International Publication No. 2016/017801 can be adopted.
As the resin powder, if a desired resin powder is commercially available, it may be used.

The liquid medium in the liquid composition of the present invention comprises an inorganic solvent such as water, an organic solvent, or the like. The liquid medium may be a mixture of two or more compatible liquid media. For example, it may be a mixture of a water-soluble organic solvent and water, or a mixture of two or more kinds of organic solvents.
The boiling point of the liquid medium is preferably 270 ° C. or lower, and a liquid medium having a boiling point of 70 to 260 ° C. is preferable.
Water is preferable as the inorganic solvent.
As the organic solvent, a known liquid medium can be used, for example, alcohols such as ethanol, nitrogen-containing compounds such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide, and diethyl. Examples thereof include ethers such as ether and dioxane, esters such as ethyl acetate, ketones such as methyl ethyl ketone, glycol ethers such as ethylene glycol monoisopropyl ether, and cellosolves such as methyl cellosolve.
The liquid medium is a compound that does not react with the polymer (X).

Specific examples of the organic solvent include the following organic solvents.
γ-Butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-pentyl ketone, methyl isobutyl ketone, methyl isopentyl ketone.
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene Glycoldiacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, pyruvate Methyl acid acid, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate.
Anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, simen, mesityrene.
Methanol, ethanol, isopropanol, butanol, methylmonoglycidyl ether, ethylmonoglycidyl ether, dimethylformamide, mineral spirit, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone.
Perfluorocarbons, hydrofluoroethers, hydrochlorofluorocarbons, hydrofluorocarbons, perfluoropolyethers, various silicone oils.

The content of the liquid medium in the liquid composition of the present invention is preferably 1 to 1000 parts by mass, more preferably 10 to 500 parts by mass, and particularly preferably 30 to 250 parts by mass with respect to 100 parts by mass of the resin powder. When the content of the liquid medium is within the above range, the coatability at the time of film formation, which will be described later, is good. Further, when the content of the liquid medium is not more than the upper limit of the above range, the amount of the liquid medium used is small, so that the appearance of the film-formed product due to the process of removing the liquid medium is unlikely to deteriorate.

The liquid composition of the present invention may contain a surfactant. The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Among them, as the surfactant, a nonionic surfactant is preferable. The surfactant may be used alone or in combination of two or more.
The surfactant in the present invention needs to have at least a fluorine-containing group and a hydrophilic group, and is not particularly limited as long as it has at least a lipophilic group and a hydrophilic group. In addition to this, lipophilic groups may be contained. By using a fluorine-based additive having at least a fluorine-containing group and a hydrophilic group, the surface tension of the solvent as a dispersion medium is lowered, the wettability to the surface of the fluororesin is improved, and the dispersibility of the fluororesin is improved. , Fluororesin-containing groups are adsorbed on the surface of the fluororesin, and the hydrophilic groups extend into the liquid medium as the dispersion medium. It becomes a thing. Examples of the fluorine-containing group include a perfluoroalkyl group and a perfluoroalkenyl group, and examples of the hydrophilic group include ethylene oxide, propylenexide, amino group, ketone group, carboxyl group and sulfone group. 1 type or 2 or more of the above, and examples of the lipophilic group include 1 type or 2 or more of an alkyl group, a phenyl group, a siloxane group and the like.
Specific examples of the fluorine-based additives that can be used include the perfluoroalkyl group-containing Futagent M series, Futagent F series, Futagent G series, Futagent P / D series, Futagent 710FL, Futagent 710FM, and Futter. Surflon series such as GENT 710FS, Fluorent 730FL, Fluorent 730LM, Fluorent 610FM, Fluorent 601AD, Fluorent 601ADH2, Fluorent 602A, Fluorent 650AC, Fluorent 681 (manufactured by Neos), Surflon S-386, etc. AGC Seimi Chemical Co., Ltd.), Mega Fuck F-553, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-557, Mega Fuck F-559, Mega Fuck F-562, Mega Fuck F-565, etc. The Megafuck series (manufactured by DIC), the Unidyne series (manufactured by Daikin Industries) such as Unidyne DS-403N, and the like can be used. The optimum surfactant is appropriately selected depending on the type of fluororesin and solvent used, but one type or a combination of two or more types can also be used. When two or more types of surfactants are used in combination, at least one type must have a fluorine-containing group and a hydrophilic group, and the remaining types do not contain a fluorine-containing group. May be good.

The liquid composition of the present invention may further contain a silicone-based defoaming agent or a fluorosilicone-based defoaming agent. Examples of the defoaming agent that can be used include silicone-based and fluorosilicone-based emulsion types, self-emulsifying types, oil types, oil compound types, solution types, powder types, solid types, etc., but in combination with the liquid medium to be used. Then, the most suitable one will be selected as appropriate. The content of the defoaming agent varies depending on the content (concentration) of the resin powder and the like, but is preferably 1% by mass or less as the active ingredient with respect to the total amount of the liquid composition.

When the liquid composition of the present invention contains a surfactant, the content of the surfactant in the liquid composition is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin powder, and is 0.2 to 20 parts by mass. 10 parts by mass is more preferable, and 0.3 to 7 parts by mass is particularly preferable. When the content of the surfactant is at least the lower limit of the above range, excellent dispersibility can be easily obtained. When the content of the surfactant is not more than the upper limit of the above range, the characteristics of the resin powder can be obtained without being affected by the characteristics of the surfactant. For example, the dielectric constant and dielectric loss tangent of a film or the like formed by using the liquid composition of the present invention can be lowered.

The liquid composition of the present invention may contain a filler. When the liquid composition of the present invention contains a filler, the dielectric constant and dielectric loss tangent of a film or the like formed by using the liquid composition of the present invention can be lowered. As the filler, an inorganic filler is preferable, and the filler described in [089] of International Publication No. 2016/017801 can be mentioned. One type of inorganic filler may be used alone, or two or more types may be used in combination.
Further, a powder composed of fine particles of a non-thermosetting resin (PTFE, a cured product of a thermosetting resin, etc.) described later can be regarded as an organic filler, and as the organic filler, PTFE powder is particularly preferable.

When the liquid composition of the present invention contains a filler, the content of the filler in the liquid composition is preferably 0.1 to 300 parts by mass, more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the resin powder. 3, 150 parts by mass is more preferable, 5 to 100 parts by mass is particularly preferable, and 10 to 60 parts by mass is most preferable. The higher the filler content, the lower the coefficient of linear expansion (CTE) of the obtained film and the better the thermal dimensionality of the film. Furthermore, the dimensional change in the heating process is small, and the molding stability is excellent.

The liquid composition of the present invention may contain a powder of a resin other than the polymer (X), or a curable or non-curable resin dissolved in a liquid medium. A resin other than the polymer (X), which is insoluble in a liquid medium, is contained in the liquid composition as fine particles (that is, as a resin powder). The resin that is insoluble in such a liquid medium and the curable or non-curable resin that is dissolved in the liquid medium are hereinafter collectively referred to as "second resin".
The second resin that is insoluble in the liquid medium may be a non-curable resin or a curable resin.
Examples of the non-curable resin include heat-meltable resins and non-meltable resins. The non-curable resin may have a reactive group capable of reacting with the functional group (i) of the polymer (X). Examples of the heat-meltable resin include a fluororesin made of a fluorine-containing polymer other than the polymer (X), a thermoplastic polyimide, and the like. Examples of the non-meltable resin include PTFE, a cured product of a curable resin, and the like, and these fine particles can also be regarded as a filler.
Examples of the curable resin include a polymer having a reactive group, an oligomer having a reactive group (low polymer), a small molecule compound, and a small molecule compound having a reactive group. The curable resin is a resin that is cured by a reaction between its own reactive groups, a reaction with the functional group (i) of the polymer (X), a reaction with a curing agent, and the like. As the curable resin, a thermosetting resin is preferable. The curable resin is preferably cured after the liquid medium is removed from the liquid composition of the present invention.
Examples of the reactive group include a carbonyl group-containing group, a hydroxy group, an amino group, an epoxy group and the like.

Examples of the second resin include thermoplastic polyimides, thermosetting polyimides, and polyamic acids which are precursors thereof. The polyamic acid usually has a reactive group capable of reacting with the functional group (i) of the polymer (X). The thermoplastic polyimide or the like does not have to have a reactive group capable of reacting with the functional group (i).
Examples of the diamine and polyvalent carboxylic acid dianhydride forming the polyamic acid include [0020] of Japanese Patent No. 5766125, [0019] of Japanese Patent No. 5766125, and [0055] of Japanese Patent Application Laid-Open No. 2012-145676. , [0057] and the like. Among them, aromatic amines such as 4,4'-diaminodiphenyl ether and 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and pyromellitic dianhydride, 3,3', 4,4. A combination with an aromatic polyvalent carboxylic dianhydride such as'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride is preferable. As the diamine and the polyvalent carboxylic acid dianhydride or a derivative thereof, one type may be used alone, or two or more types may be used in combination.

In the case of a heat-meltable second resin or a second resin that is cured to become a heat-meltable resin, the heat-meltable resin preferably has a melting point of 280 ° C. or higher. As a result, in a film or the like formed of a liquid composition, swelling (foaming) due to heat when exposed to an atmosphere corresponding to solder reflow is likely to be suppressed.

The second resin may also be a resin made of a polymer that is not heat-meltable. Non-heat-meltable resins such as non-meltable resins such as PTFE and resins composed of cured products of thermosetting resins are non-meltable resins in a liquid medium, and like the inorganic filler, fine particles are contained in the liquid medium. It is dispersed in a shape.

Examples of the thermosetting resin include epoxy resin, acrylic resin, phenol resin, polyester resin, polyolefin resin, modified polyphenylene ether resin, polyfunctional cyanate ester resin, polyfunctional maleimide-cyanic acid ester resin, polyfunctional maleimide resin, and vinyl. Examples thereof include ester resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, melamine-urea cocondensate resin, and fluororesin having a reactive group (however, polymer (X) is excluded). Among them, epoxy resin, acrylic resin, bismaleimide resin, and modified polyphenylene ether resin are preferable, and epoxy resin and modified polyphenylene ether resin are particularly preferable, as the thermosetting resin from the viewpoint of being useful for printed substrate applications. One type of thermosetting resin may be used alone, or two or more types may be used in combination.

The epoxy resin is not particularly limited as long as it is an epoxy resin used for forming various substrate materials for printed circuit boards. Specifically, naphthalene type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, cresol novolac type Epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, aralkyl type epoxy resin, biphenol type epoxy resin, dicyclopentadiene type epoxy resin, trishydroxyphenylmethane type epoxy compound, phenols and aromatics having phenolic hydroxyl groups Examples thereof include an epoxidized product of a condensate with an aldehyde, a diglycidyl etherified product of bisphenol, a diglycidyl etherified product of naphthalenediol, a glycidyl etherified product of phenols, a diglycidyl etherified product of alcohols, and triglycidyl isocyanurate. In addition to those listed above, various glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, and oxidized epoxy resins may be used, and phosphorus-modified epoxy resins and the like may also be used. It is possible. The epoxy resin may be used alone or in combination of two or more. In particular, from the viewpoint of excellent curability, it is preferable to use an epoxy resin having two or more epoxy groups in one molecule.

The weight average molecular weight of the epoxy resin is preferably 100 to 1000000, more preferably 1000 to 100,000. When the weight average molecular weight of the epoxy resin is within the above range, the interlayer adhesion between the film or the like formed by the liquid composition and another material (metal or the like) is excellent.
The weight average molecular weight of the epoxy resin is measured by gel permeation chromatography (GPC).

Examples of the bismaleimide resin include a resin composition (BT resin) in which a bisphenol A type cyanate ester resin and a bismaleimide compound are used in combination, as described in Japanese Patent Application Laid-Open No. 7-70315, and International Publication No. 2013/0083667. Examples thereof include those described in the invention described in the item and the background technology thereof.

When a thermosetting resin is used as the second resin, the liquid composition of the present invention may contain a curing agent. Examples of the curing agent include thermosetting agents (melamine resin, urethane resin, etc.), epoxy curing agents (novolac type phenol resin, isophthalic acid dihydrazide, adipic acid dihydrazide, etc.) and the like.

The content of the resin powder in the liquid composition of the present invention is preferably 5 to 500 parts by mass, preferably 10 to 400 parts by mass, and particularly 20 to 300 parts by mass with respect to 100 parts by mass of the second resin. preferable. When the content of the resin powder is at least the lower limit of the above range, a film or the like formed by using the liquid composition has excellent electrical characteristics. When the content of the resin powder is not more than the upper limit of the above range, the resin powder is likely to be uniformly dispersed in the liquid composition, and the film or the like formed by using the liquid composition is excellent in mechanical strength.

When the liquid composition of the present invention contains the second resin, the content of the liquid medium in the liquid composition is preferably 1 to 1000 parts by mass with respect to 100 parts by mass in total of the resin powder and the second resin. , 10 to 500 parts by mass is more preferable, and 30 to 250 parts by mass is particularly preferable. When the content of the liquid medium is not more than the lower limit of the above range, the viscosity of the liquid composition is not too high, and the coatability at the time of film formation described later is good. When the content of the liquid medium is not more than the upper limit of the above range, the viscosity of the liquid composition is not too low, the coatability at the time of film formation is good, and the amount of the liquid medium used is small. Poor appearance of the film-formed product due to the removal process is unlikely to occur.
When the second resin is blended together with the liquid medium (for example, when the dispersion liquid or solution of the second resin is blended in the composition containing the resin powder and the liquid medium), it is contained in the liquid composition. The content of the liquid medium is the total content of the liquid media.

When the liquid composition of the present invention contains a curing agent, the content of the curing agent in the liquid composition is preferably 0.5 to 2.0 equivalents with respect to the amount of reactive groups of the thermosetting resin. 0.8 to 1.2 equivalents are more preferred.

The method for producing the liquid composition of the present invention is not particularly limited, and examples thereof include a method in which a resin powder, other components used as necessary, and a liquid medium are mixed and stirred. As the means for mixing and stirring, for example, it is preferable to use a disperser such as a homomixer, a high-speed stirrer, an ultrasonic disperser, a homogenizer, a wet ball mill, a bead mill, or a wet jet mill.
When the liquid composition of the present invention contains a surfactant, in the case of the liquid composition of the present invention containing a surfactant, the resin powder, the surfactant and the liquid medium are dispersed by using a disperser. To obtain a stable liquid composition in which the average particle size of the resin powder by the dynamic light scattering method in the dispersed state is 0.3 to 6 μm or less and excellent in storage stability and redispersibility after long-term storage. Can be done.

When the liquid composition of the present invention is used, it can be uniformly dispersed in a thermoplastic resin or the like without scattering the resin powder, as compared with the case where the resin powder is treated as a powder.
Further, in the liquid composition of the present invention, since the resin powder in which the average particle size and D90 are controlled in a specific range is dispersed in the liquid medium, the dispersibility is excellent. Therefore, when a film, a laminate, or the like is formed using the liquid composition of the present invention, the electrical characteristics are deteriorated due to the non-uniform dispersion of the resin powder in them, and the adhesive force of other base materials is deteriorated. It is possible to suppress problems such as.

When the liquid composition of the present invention contains a filler as another component, the liquid composition of the present invention can be produced by dispersing the filler powder together with the resin powder in a liquid medium. The dispersion liquid of the filler may be blended with the resin powder in the liquid medium, or the dispersion liquid of the filler and the dispersion liquid of the resin powder may be mixed. As the liquid medium in the dispersion liquid of the filler, the liquid medium can be used. When the liquid mediums in the dispersion liquid of the filler or non-heat-meltable resin and the dispersion liquid of the resin powder are different, the liquid media may be compatible.

When the other component is the second resin, the resin insoluble in the liquid medium can produce the liquid composition of the present invention by dispersing the resin powder together with the resin powder in the liquid medium. Further, it can be produced by mixing a second resin dispersion liquid previously dispersed in a liquid medium with a resin powder dispersion liquid, or by dispersing a resin powder in a second resin dispersion liquid. ..
When the second resin is a resin soluble in a liquid medium, the liquid composition of the present invention can be produced by blending and dissolving the second resin in a dispersion of resin powder. The second resin can be produced by mixing it with a solution of a liquid medium, or can be produced by dispersing the resin powder in the solution.
The method for mixing the dispersion liquid of the resin powder and the liquid containing other components is not particularly limited, and examples thereof include a method using a known stirrer. When the liquid composition contains a filler, a curing agent, etc., they may be added to the dispersion liquid before mixing, may be added to a liquid containing other components before mixing, or may be added to the mixed liquid after mixing. It may be added.

The liquid composition of the present invention can be used, for example, in the production of films, fiber-reinforced films, prepregs, and laminates, which will be described later.
The liquid composition of the present invention can also be used for forming an insulating layer of a flat conductor. For example, when forming an insulating layer containing any resin of polyamide-imide, polyimide, or polyesterimide as a main component, a liquid composition obtained by blending the liquid composition of the present invention with an insulating coating material which is a liquid containing the resin. It is possible to reduce the dielectric constant of the insulating layer by using. The decrease in the dielectric constant of the insulating layer can be achieved by adding a resin powder to the insulating paint, but from the viewpoint of dispersibility, it is preferable to use a liquid composition obtained by blending the liquid composition of the present invention with the insulating paint. Specific examples of the insulating layer include the insulating film described in JP2013-191356A.

The liquid composition of the present invention can also be used for forming a seamless belt. For example, by using a liquid composition obtained by blending the liquid composition of the present invention with a liquid containing a polyimide resin and a conductive filler, the recording medium (paper) is excellent in transportability and cleanability. We can provide seamless belts. A seamless belt having excellent transportability and cleanability of a recording medium can be obtained by adding resin powder to a liquid containing a polyimide resin and a conductive filler, but from the viewpoint of dispersibility, the liquid of the present invention can be obtained. It is preferable to use a liquid composition containing the liquid composition. Examples of the seamless belt include those described in Japanese Patent Application Laid-Open No. 2011-240616.

[Film manufacturing method]
The method for producing a film of the present invention is characterized in that the liquid composition of the present invention is formed into a film and the liquid medium is removed. The film-forming method is preferably applied on the surface of the carrier, and by applying on the carrier, a film made of a liquid composition is formed. After the film of the liquid composition was formed, the liquid medium was volatilized by a method such as heating the film of the liquid composition, and the solid film from which the liquid medium was removed or at least a part of the liquid medium was removed. A non-fluid film is formed. Hereinafter, the removal of the liquid medium is also referred to as "drying", and the operation of applying is also referred to as "coating".
The film forming method of the liquid composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method, a bar coating method, a gravure coating method, a micro gravure coating method, a gravure offset method, a knife coating method, and a kiss coating method. Examples thereof include known wet coating methods such as a method, a bar coating method, a die coating method, a fountain Mayer bar method, and a slot die coating method.

In the drying, it is not always necessary to completely remove the liquid medium, and the drying may be performed until the coating film can maintain the film shape stably. In drying, it is preferable to remove 50% by mass or more of the liquid medium contained in the liquid composition.
The drying method is not particularly limited, and examples thereof include a method of heating in an oven, a method of heating in a continuous drying furnace, a method of heating by irradiation with heat rays such as infrared rays, and the like.
The drying temperature may be in the range where bubbles do not occur when the liquid medium is removed, and is preferably 50 to 250 ° C, more preferably 70 to 220 ° C, for example.
The drying time is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes.
Drying may be carried out in one step or in two or more steps at different temperatures.

As a method for producing a film of the present invention, it is preferable to separately heat the dried film or heat the film after drying to melt the polymer (X). By melting the polymer (X), the individual particles of the resin powder can be melted and integrated to form a homogeneous resin film. When the liquid composition of the present invention has a filler, a resin film in which the filler is uniformly dispersed can be obtained. When the liquid composition of the present invention contains a heat-meltable second resin, a resin film composed of a melt-blended product of the polymer (X) and the second resin can be produced. When the thermosetting second resin is contained, a resin film composed of the polymer (X) and a cured product of the second resin can be produced. Heating of the resin film is not limited to heating from the exposed surface of the film, and heating can also be performed from the carrier side. Further, heating for melting the polymer (X) can also be performed under pressure, and a more homogeneous film can be obtained by melting under heating and pressurization.

Examples of the heating method for melting the polymer (X) include oven heating, heat ray irradiation heating, heating by a continuous drying furnace, heating by a hot plate or a heat roll, and the like.
The heating for melting the polymer (X) can also be performed in a closed system. In drying a coating film in which a liquid medium is present, one side of the film needs to be an open surface because the vaporized liquid medium must be removed from the film. On the other hand, heating after the liquid medium is sufficiently removed from the film does not require removal of the liquid medium, so that, for example, pressure can be applied between two heating plates to produce a highly homogeneous film.
The heating temperature for melting the polymer (X) is preferably 270 to 400 ° C, more preferably 310 to 370 ° C.
The heating time is preferably 1 to 300 minutes, more preferably 3 to 60 minutes.

In particular, a heat ray irradiation heating method using far infrared rays having an effective wavelength band of 2 to 20 μm is preferable as a method for obtaining a molten resin film in which uniform melting of the resin is achieved and few particles with insufficient melting remain. The effective wavelength band of the far infrared rays to be irradiated is more preferably 3 to 7 μm. It is also possible to heat by combining far-infrared heating and hot air heating.
In addition, heat radiation is emitted from the heating plate that emits far infrared rays toward the film surface, and heat treatment is performed more efficiently by heating while injecting an inert gas. When heating from the carrier side, it is similarly preferable to inject the inert gas onto the film surface side. When the object to be heated is oxidized, the oxygen concentration in the atmosphere on the film surface side is preferably 500 ppm to 100 ppm, more preferably 300 ppm to 200 ppm when radiating far infrared rays.

Depending on the use of the film, such as when the film produced by the production method of the present invention is used as a material for a laminate described later, the polymer (X) in the resin powder in the liquid composition of the present invention is sufficient. The film may be in an unmelted state. Such films can be used in applications where the film is heated to a homogeneous polymer (X). Further, even in the liquid composition of the present invention containing the second resin, the second resin may not be sufficiently melted depending on the use of the film (such as in the case of prepreg production described later), and is a thermosetting resin. The curable resin such as, etc. does not have to be sufficiently cured.
In films used for purposes other than the above, the meltable second resin is preferably melted and homogenized, and the curable resin is preferably sufficiently cured. For example, in the case of a polyamic acid, the heating after drying is preferably heated to a temperature at which the polyamic acid becomes polyimide (for example, 350 to 550 ° C.), and in the case of an epoxy resin, for example, its curing temperature (for example, 50). It is preferable to heat to ~ 250 ° C.).

A film is obtained by separating the film formed on the carrier from the carrier. By using a carrier having a non-adhesive surface as the carrier, it can be easily separated. Further, as the carrier having an adhesive surface, it is preferable to use a carrier that has been subjected to a surface treatment or the like to reduce the adhesiveness. Further, in the case of a carrier having a highly adhesive surface, the carrier can be removed by means such as dissolving the carrier. For example, in the case of a metal carrier, the carrier can be removed by etching or the like.

The film obtained by the method for producing a film of the present invention can be used for producing a metal laminate and a printed circuit board. As the film used for these applications, a film containing only a resin powder and a liquid medium, or a film obtained from a liquid composition further containing a surfactant is preferable. In some cases, it may be a liquid composition containing a filler.
It should be noted that the film manufacturing method of the present invention can also be used to manufacture a fiber-reinforced film or a film called a prepreg, which will be described later. Further, the laminate can be produced by the same method as the method for producing a film of the present invention, except that it is not separated from the carrier. In the method for producing a laminate of the present invention, the carrier that is not separated is referred to as a base material.

Except for the fiber-reinforced film and prepreg described later (that is, those containing reinforcing fibers), the thickness of the film produced by the production method of the present invention is preferably 1 to 3000 μm. For printed circuit board applications, the film thickness is more preferably 3 to 2000 μm, even more preferably 5 to 1000 μm, and particularly preferably 6 to 500 μm.
The relative permittivity of the film is preferably 2.0 to 3.5, and particularly preferably 2.0 to 3.0. When the relative permittivity is not more than the upper limit of the above range, it is useful for applications requiring a low dielectric constant such as printed circuit board applications. When the relative permittivity is at least the lower limit of the above range, both the electrical characteristics and the adhesive fusion property are excellent.
Except for the fiber-reinforced film and prepreg described later, the film produced by the production method of the present invention has a coefficient of thermal expansion (shrinkage) in the MD direction (coating direction of the liquid composition) and the TD direction (vertical direction in the MD direction). X / y, which is the ratio of (hereinafter, also referred to as thermal expansion (contraction) change ratio), is preferably 1.0 to 1.4, and more preferably 1.0 to 1.3. When x / y is in the above range, warpage when forming the metal laminated board and the printed circuit board is suppressed, which is preferable. The coefficient of change in thermal expansion (contraction) is the ratio between the x direction (large coefficient of thermal expansion (contraction)) and the y direction (small coefficient of thermal expansion (contraction)), and is represented by "x / y".
Further, it is preferable that the arithmetic average roughness Ra of the surface of the film is less than the resin thickness and 2.0 μm or more. As a result, when a laminated object such as a prepreg is bonded to the surface by a hot press, excellent adhesion between the film and the laminated object can be obtained.
Ra is preferably 2.0 to 30 μm, more preferably 2.1 to 10 μm, and even more preferably 2.2 to 5 μm. When Ra is at least the lower limit of the above range, the adhesion between the film and the object to be laminated is excellent. When Ra is equal to or less than the upper limit of the above range, through holes are unlikely to be formed in the film.

According to the method for producing a film of the present invention, the liquid composition of the present invention can be impregnated into a reinforcing fiber base material arranged on a carrier, dried, and then heated to produce a fiber-reinforced film.
Examples of the reinforcing fiber include inorganic fiber, metal fiber, organic fiber and the like.
Examples of the inorganic fiber include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, boron fiber and the like.
Examples of the metal fiber include aluminum fiber, brass fiber, stainless steel fiber and the like.
Examples of the organic fiber include aromatic polyamide fiber, polyaramid fiber, polyparaphenylene benzoxazole (PBO) fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber, polyethylene fiber and the like.
As the reinforcing fiber forming the reinforcing fiber base material, glass fiber, aramid fiber and carbon fiber are preferable. As the reinforcing fiber, carbon fiber is particularly preferable because it has a small specific gravity, high strength, and a high elastic modulus. The reinforcing fiber may be one that has been surface-treated. As the reinforcing fiber, one type may be used alone, or two or more types may be used in combination.
The reinforcing fiber may be one that has been surface-treated. Further, in the use of printed circuit boards, glass fiber is preferable as the reinforcing fiber.

As the form of the reinforcing fiber base material, one processed into a sheet shape is preferable from the viewpoint of the mechanical properties of the fiber reinforced film. Specific examples thereof include a cloth made by weaving a bundle of reinforcing fibers made of a plurality of reinforcing fibers, a base material in which a plurality of reinforcing fibers are aligned in one direction, and a stack of them. The reinforcing fibers need not be continuous over the entire length in the length direction or the entire width in the width direction of the reinforcing fiber sheet, and may be divided in the middle.
As the reinforcing fiber, continuous long fibers having a length of 10 mm or more are preferable. The reinforcing fibers need not be continuous over the entire length in the length direction or the entire width in the width direction of the reinforcing fiber sheet, and may be divided in the middle.

After impregnating the reinforcing fiber base material with the liquid composition of the present invention, it is dried to remove at least a part of the liquid medium, and further heated. Drying and heating after impregnation can be performed in the same manner as described above. In the fiber-reinforced film, the resin derived from the resin powder contained therein may not be sufficiently melted as long as the shape of the fiber-reinforced film is maintained. Such a fiber-reinforced film can be used as a molding material, and can be heated and pressed together with molding to produce a molded product.

The fiber-reinforced film obtained by the production method of the present invention can be used for producing a metal laminate and a printed circuit board.
The thickness of the fiber reinforced film is preferably 1 to 3000 μm. For printed circuit board applications, the thickness of the fiber reinforced film is more preferably 3 to 2000 μm, further preferably 5 to 1000 μm, and particularly preferably 6 to 500 μm.

The relative permittivity of the fiber-reinforced film is preferably 2.0 to 3.5, and particularly preferably 2.0 to 3.0. When the relative permittivity is not more than the upper limit of the above range, it is useful for applications requiring a low dielectric constant such as printed circuit board applications. When the relative permittivity is at least the lower limit of the above range, both electrical characteristics and fusion properties are excellent.

According to the method for producing a film of the present invention, the liquid composition of the present invention can be impregnated into a reinforcing fiber base material arranged on a carrier and dried to produce a prepreg. The production of the prepreg can be carried out in the same manner as the production of the fiber-reinforced film, except that the prepreg is not heated after drying or is not sufficiently heated. That is, the prepreg is a film containing reinforcing fibers, an unmelted (or not sufficiently melted) resin powder, and an uncured curable resin which is a second resin.
The liquid composition used in the production of prepreg contains an uncured curable resin as a second resin. As the uncured curable resin, a thermosetting resin that is solid at room temperature is preferable. In the case of a thermosetting resin that is liquid at room temperature, it can be partially cured by heating after drying in prepreg production to obtain a solid resin that can be thermally cured.

In the drying in the prepreg production, the liquid medium may remain. In the prepreg, it is preferable that 70% by mass or more of the liquid medium contained in the liquid composition is removed.
When the liquid composition of the present invention contains a thermosetting resin as the second resin, the thermosetting resin is easily cured by heating after drying, so that the heating after drying does not cure the thermosetting resin. It is preferable to carry out at temperature. However, as described above, it may be preferable to partially cure. In this case, since the polymer (X) is not usually melted, it is preferable to perform the prepreg at a temperature at which the polymer (X) is melted when it is cured.

The prepreg obtained by the production method of the present invention can be used as a molding material, and a molded product can be produced by heating and pressurizing with molding. For example, it can be used in the manufacture of metal laminates and printed circuit boards. Further, the preprig obtained by the manufacturing method of the present invention can be used for applications other than electronic components such as printed circuit boards. For example, it can be used as a material for sheet piles that are required to be durable and lightweight in quay construction, and as a material for manufacturing members for various uses such as aircraft, automobiles, ships, wind turbines, and sporting tools.

The relative permittivity of the prepreg is preferably 2.0 to 4.0, and particularly preferably 2.0 to 3.5. When the relative permittivity is not more than the upper limit of the above range, it is useful for applications requiring a low dielectric constant such as printed circuit board applications. When the relative permittivity is at least the lower limit of the above range, both electrical characteristics and fusion properties are excellent.

[Manufacturing method of laminated body]
The method for producing a laminated body of the present invention is characterized in that the above-mentioned liquid composition of the present invention is formed into a film on a base material and the liquid medium is removed to form a resin layer laminated on the base material. do.
This production method corresponds to the method for producing a film and a single laminate without separating the carrier and the film after drying or after drying and heating. In the method for producing a laminate, the portion corresponding to the carrier is referred to as a base material, and the portion corresponding to the film is referred to as a "resin layer". The resin layer may be a portion corresponding to the fiber-reinforced film, and the prepreg may be a portion corresponding to.

The resin layer formed by the method for producing a laminate of the present invention may be formed on only one side in the thickness direction of the base material, or may be formed on both sides. It is preferable to form resin layers on both sides of the base material in that it is easy to suppress the warp of the laminated body and it is easy to obtain a metal laminated plate having excellent electrical reliability. The resin layer is preferably in the form of a film.

When forming resin layers on both sides of a base material, the liquid composition may be applied and dried on one surface of the base material, and then the liquid composition may be applied and dried on the other surface. preferable. The heating after drying may be performed after the liquid composition is applied and dried on both sides of the base material, from the application of the dispersion liquid or the liquid composition to the heating on one surface of the base material. After that, the liquid composition may be applied to the other surface to heat.

The thickness of the resin layer in the laminated body is preferably 0.5 to 30 μm when the filler contained in the resin layer is less than 10% by volume. For printed circuit board applications, the thickness of the resin layer is more preferably 0.5 to 25 μm, even more preferably 1 to 20 μm, and particularly preferably 2 to 15 μm. In a preferable range, the warp of the laminated body is suppressed. When the filler contained in the resin layer is 10% by volume or more, 0.5 to 3000 μm is preferable. For printed circuit board applications, the thickness of the resin layer is more preferably 1 to 1500 μm, even more preferably 3 to 500 μm, and particularly preferably 2 to 100 μm.
In the case of a laminate having resin layers on both sides of the base material, the composition and thickness of the respective resin layers may be the same or different. From the viewpoint of suppressing warpage of the laminated body, it is preferable that the composition and thickness of the respective resin layers are the same.

The relative permittivity of the resin layer is preferably 2.0 to 3.5, and particularly preferably 2.0 to 3.0. When the relative permittivity is not more than the upper limit of the above range, it is useful for applications requiring a low dielectric constant such as printed circuit board applications. When the relative permittivity is at least the lower limit of the above range, both electrical characteristics and fusion properties are excellent.
When the base material is made of a non-conductive material such as a heat-resistant resin, the relative permittivity of the entire laminate is preferably in the above range.

When the laminate obtained by the production method of the present invention is used for laminating an object to be laminated such as a film or a sheet on the surface of the resin layer, the bonding strength thereof is increased and bubbles and the like are prevented from remaining. Therefore, the exposed surface of the resin layer is preferably a surface having high smoothness.
The object to be laminated may be a laminate obtained by the production method of the present invention. In this case, the base material surface or the resin layer surface of another laminated body is laminated on the exposed surface of the resin layer. When laminating the resin surfaces, the laminating object may be interposed between the resin layer surfaces.
In order to improve the smoothness of the exposed surface of the resin layer, it is preferable to carry out the process at a temperature at which the film after drying can be sufficiently melted and pressurize with a heating plate, a heating roll or the like.
The arithmetic mean roughness Ra of the surface of the exposed surface of the resin layer of the obtained laminate is less than the thickness of the resin layer, and is preferably 2.0 μm or more. As a result, when the objects to be laminated are laminated by a hot press or the like, excellent adhesion between the resin layer and the objects to be laminated can be obtained.
Ra is less than the thickness of the resin layer, preferably 2.0 to 30 μm, more preferably 2.0 to 15 μm, further preferably 2.1 to 12 μm, particularly preferably 2.1 to 10 μm. Most preferably 2 to 8 μm. When Ra is equal to or higher than the lower limit of the above range, the adhesion between the resin layer and the object to be laminated is excellent. When Ra is equal to or less than the upper limit of the above range, the resin layer can be laminated without forming through holes.

Further, when the laminate obtained by the production method of the present invention is used for laminating an object to be laminated such as a film or a sheet on the surface of the resin layer, the laminate is manufactured in order to increase the bonding strength. The surface of the post-resin layer may be subjected to surface treatment such as corona discharge treatment and plasma treatment. Plasma treatment is particularly preferable. The surface treatment for increasing the bonding strength can be performed under known conditions.

The plasma irradiation device used for plasma processing is not particularly limited, and is limited to a high frequency induction method, a capacitively coupled electrode method, a corona discharge electrode-plasma jet method, a parallel plate type, a remote plasma type, an atmospheric pressure plasma type, and an ICP type high density plasma. Examples include devices that employ molds and the like.
The gas used for the plasma treatment is not particularly limited, and examples thereof include oxygen, nitrogen, a rare gas (argon), hydrogen, and ammonia, and a rare gas or nitrogen is preferable. These may be used individually by 1 type, or may be used by mixing 2 or more types.
The atmosphere of the plasma treatment is preferably an atmosphere having a volume fraction of rare gas or nitrogen gas of 50% by volume or more, more preferably 70% by volume or more, further preferably 90% by volume or more, and an atmosphere of 100% by volume. Is particularly preferable. When the volume fraction of the rare gas or nitrogen gas is at least the lower limit value, the surface of the fluororesin film can be easily renewed to a plasma-treated surface having an arithmetic mean roughness Ra of 2.0 μm or more.
The gas flow rate in the plasma treatment is not particularly limited.

In the plasma treatment, the Ra on the film surface increases as the treatment is performed, but if the treatment is performed too much, the Ra that has once increased tends to decrease again. Therefore, the processing time is set by controlling the electron energy (about 1 to 10 eV) generated by adjusting the gap between electrodes, the output of the device, etc. so that the processing does not become excessive.

The base material is not particularly limited, and examples thereof include a metal film, a heat-resistant resin film, and a metal-deposited heat-resistant resin film.
The metal constituting the metal film can be appropriately selected depending on the intended use, and examples thereof include copper or a copper alloy, stainless steel or an alloy thereof, titanium or an alloy thereof, and the like. As the metal film, a copper film such as a rolled copper foil or an electrolytic copper foil is preferable. A rust preventive layer (for example, an oxide film such as chromate) or a heat-resistant layer may be formed on the surface of the metal film. Further, in order to improve the adhesion with the resin layer, the surface of the metal film may be treated with a coupling agent or the like.
The thickness of the metal film is not particularly limited, and a thickness capable of exhibiting sufficient functions may be selected according to the application.
Examples of the metal-deposited heat-resistant resin film include a film in which the above metal is vapor-deposited on one or both sides of the following heat-resistant resin film by a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method.

The heat-resistant resin film is a film containing one or more of heat-resistant resins. However, the heat-resistant resin film does not contain a fluorine-containing polymer. The heat-resistant resin film may be a single-layer film or a multilayer film.
The heat-resistant resin means a polymer compound having a melting point of 280 ° C. or higher, or a polymer compound having a maximum continuous use temperature of 121 ° C. or higher as defined by JIS C 4003: 2010 (IEC 60085: 2007). Examples of the heat-resistant resin include polyimide (aromatic polyimide, etc.), polyarylate, polysulfone, polyallyl sulfone (polyether sulfone, etc.), aromatic polyamide, aromatic polyether amide, polyphenylensulfide, and polyallyl ether. Examples thereof include ketones, polyamideimides, and liquid crystal polyesters.
As the heat-resistant resin film, a polyimide film and a liquid crystal polyester are preferable. If necessary, the polyimide film may contain additives as long as the effects of the present invention are not impaired. Further, the liquid crystal polyester film is preferable from the viewpoint of improving the electrical characteristics. The heat-resistant resin film may be subjected to surface treatment such as corona discharge treatment and plasma treatment on the surface forming the resin layer.

The laminate obtained by the production method of the present invention is produced from a liquid composition containing no second resin, or is a second resin having heat-sealing properties or a second resin having heat-sealing properties. In the case of a liquid composition containing the above resin, it is preferable to melt the resin powder containing the polymer (X) in the production of the laminate to obtain a laminate having a heat-sealing resin layer. It is preferable that the resin powder is melted at a sufficiently high temperature so that unmelted particles do not remain, and that the resin powder is pressurized at the same time as heating.
When heating or pressurization is insufficient, even if the entire resin powder particles are melted, optically non-uniform parts (granular substances or the like) may be formed in the resin layer formed by subsequent cooling. It is presumed that this is caused by the non-uniform crystallization and agglutination of the resin. In the present invention, this optically non-uniform portion is referred to as a "foreign substance". When foreign matter is generated, the number of foreign matter having a size exceeding 30 μm is preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less per ^{10 cm 2.} When the number of foreign substances is not more than the upper limit of the above range, the adhesive strength between the resin layer and the base material is excellent. Foreign matter may also be produced in the film production of the present invention.
It was obtained when the laminate obtained by the production method of the present invention had particles of resin powder that were not sufficiently melted or a second resin that was curable (for example, when the resin layer was a prepreg layer). The laminate can be used for laminating an object to be laminated on the resin layer surface by heating and pressurizing or the like, and can also be used for manufacturing a molded product by heating and pressurizing or the like.

The obtained laminated body can be used as a member for manufacturing a molded body or for various purposes. In the case of this laminated body, the object to be laminated can be further laminated on the resin layer surface by heating and pressurizing or the like.
Since the resin layer in the laminate obtained by the production method of the present invention is a resin layer containing the polymer (X), it is excellent in moldability and has high melt adhesion, so that the object to be laminated is laminated on the resin surface. If this is the case, the bonding strength of the laminated surface is high. Further, even when a plurality of laminated bodies obtained by the production method of the present invention are laminated, the bonding strength between the laminated surface between the base material surface and the resin layer and the laminated surface between the resin layer surfaces is high.

As the laminate obtained by the production method of the present invention, a laminate having a resin layer on one side or both sides of a metal substrate is preferable. In particular, a laminate using a copper foil as a base material is preferable. The resin layer may have reinforcing fibers or may be a layer of prepreg (that is, a resin layer containing reinforcing fibers and an uncured curable resin).
The laminate having a copper foil layer obtained by the method for producing a laminate of the present invention can also be a laminate having a plurality of copper foil layers by laminating a plurality of the laminates. When the laminate having the copper foil layer has a resin layer on one side or both sides thereof, it is preferable to laminate the copper foil layer on the surface of the resin layer. A laminate having a copper foil layer or a laminate thereof obtained by the method for producing a laminate of the present invention can be used as a flexible copper-clad laminate or a rigid copper-clad laminate.
Hereinafter, the method for producing a laminate of the present invention will be further described by taking the production of a laminate having a copper foil layer as an example.

The laminate having a copper foil layer uses a copper foil as a base material, and the liquid composition of the present invention is applied to one side of the copper foil to form a film of the liquid composition, and then the liquid medium is removed by heating and drying. Then, it can be continuously heated to melt the resin powder and then cooled to form a uniform resin layer without unmelted particles. As described above, resin layers can be formed on both sides of the copper foil.
The formation of a film of the liquid composition, heat drying, and melting of the resin powder can be performed under the above conditions. For example, when heating after drying is performed by heating with a hot roll, the laminated body of the unmelted resin layer after drying and the copper foil is brought into contact with the heat-resistant roll and conveyed while irradiating far infrared rays to carry the unmelted resin layer. Can be a molten resin layer. The transport speed of the roll is not particularly limited, but for example, when a heating furnace having a length of 4.7 m is used, it is preferably 4.7 m / min to 0.31 m / min. In order to efficiently heat the entire film in a shorter time, the temperature can be set from 4.7 m / min to 2.45 m / min when a heating furnace having a length of 2.45 m is used.
The heating temperature is not particularly limited, but is preferably 330 to 380 ° C., more preferably 350 to 370 ° C., assuming that the residence time of the heating furnace is 1 minute. The temperature can be lowered by lengthening the staying time.
The thickness of the resin layer of the produced laminate is preferably 15 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less. If it is equal to or less than the upper limit of the above range, warpage can be suppressed even in the case of an asymmetric layer structure of a resin layer / copper foil. The warpage rate of the laminated body is preferably 25% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 7% or less. When the warp is not more than the upper limit, the handling property is excellent in the molding process when processing the printed circuit board, and the dielectric property as the printed circuit board is excellent.
Further, a liquid composition containing a filler such as silica or PTFE, a TFE / PAVE copolymer, a TFE / HFP copolymer, polychlorotrifluoroethylene (hereinafter, also referred to as "PCTFE") or the like as a second resin, etc. By using a liquid composition containing a fluororesin (however, excluding the polymer (X)), warpage can be further suppressed.

Further, using the liquid composition of the present invention containing a thermosetting resin as the second resin, a laminate having a resin layer containing a cured thermosetting resin and a copper foil layer can also be produced. The liquid composition may contain a filler, and the fiber-reinforced resin layer may be formed by using reinforcing fibers. In this case, the thickness of the resin layer is preferably 200 μm or less, more preferably 100 μm or less. When the thickness of the resin layer is 200 μm or less, it is possible to form an electronic circuit having excellent workability and connection reliability in hole drilling when the printed circuit board is machined. Further, by including the filler in the resin layer, the warp can be further suppressed.

In the production of a laminate having a copper foil layer, the coefficient of linear expansion in the thickness direction (Z direction) can be reduced by performing an annealing treatment. As a result, it is possible to reduce the peeling between the interface between the base material and the resin layer and the variation in the electrical characteristics of the substrate due to the uneven thickness in the plane of the laminated body. As for the annealing conditions, the temperature is preferably 80 to 190 ° C., more preferably 100 ° C. to 185 ° C., and particularly preferably 120 ° C. to 180 ° C. In terms of time, 10 minutes to 300 minutes is preferable, 20 minutes to 200 minutes is more preferable, and 30 minutes to 120 minutes is particularly preferable. If the annealing temperature and time conditions are not less than the lower limit value, the linear expansion coefficient can be sufficiently reduced, and if it is not more than the upper limit value, the linear expansion coefficient can be reduced without thermal deterioration. The annealing pressure is preferably 0.001 MPa to 0.030 MPa, more preferably 0.003 MPa to 0.020 MPa, and particularly preferably 0.005 MPa to 0.015 MPa. If it is at least the lower limit, the coefficient of linear expansion can be reduced. If it is not more than the upper limit value, the coefficient of linear expansion can be reduced without compressing the base material.

By the method for producing a laminate of the present invention, a laminate using a metal base material other than copper foil can also be produced. For example, a resin layer can be formed on one side or both sides of the titanium foil to produce a laminate having the titanium foil and the resin layer. The thickness of the resin layer is preferably 10 μm or less. By laminating the fiber-reinforced composite material on the resin layer side of such a laminated body, a molded product having a layer structure such as a titanium foil / resin layer / fiber-reinforced composite material can be obtained. As the fiber-reinforced composite material to be laminated, a carbon fiber-reinforced composite material is particularly preferable.

[Use of film and laminate]
A laminate having the same structure as the laminate obtained by the method for producing a laminate of the present invention can be produced by a method other than the method for producing a laminate of the present invention. For example, the film obtained by the method for producing a film of the present invention can be laminated with a film or sheet corresponding to a base material to produce a laminate having a structure similar to that of the laminate. Further, in the method for producing a laminate of the present invention, it is difficult to produce a laminate having both sides as a base material (because it is difficult to remove a liquid medium from the liquid composition between the base materials). By using the film obtained by the method for producing a film of the present invention, a laminate having both sides as a base material can be produced.
Further, it is also possible to produce a laminate having both sides as a substrate by laminating an object to be laminated corresponding to a base material on the surface of the resin layer of the laminate obtained by the method for producing a laminate of the present invention.
Hereinafter, a laminate having at least one metal layer and a resin layer (resin layer having a polymer (X)) (hereinafter, also referred to as “metal laminate”) will be taken as an example, and obtained by the production method of the present invention. An example of using the obtained film or laminate will be described.
The metal laminate is the weight of the film obtained by the method for producing a film of the present invention (including a fiber-reinforced film and a prepreg film) or the laminate obtained by the method for producing a laminate of the present invention. A metal layer can be formed on the surface of the resin layer containing the coalesced (X) to obtain a metal laminated plate.
Examples of the method of forming the metal layer on one side or both sides of the film or laminate include a method of laminating the film or laminate and the metal foil, a method of depositing metal on the surface of the resin layer of the film or laminate, and the like. Be done. Examples of the laminating method include thermal laminating and the like. Examples of the metal vapor deposition method include a vacuum deposition method, a sputtering method, and an ion plating method.

Examples of the laminated structure of the manufactured metal laminate include a film / metal layer, a metal layer / film / metal layer, and the like when the film obtained by the production method of the present invention is used. When the laminate obtained by the production method of the present invention is used, examples of the laminated structure of the metal laminate include a laminate layer / metal layer, a metal layer / laminate layer / metal layer, and the like. However, the layer in the laminate in contact with the metal layer is a resin layer.

The film or laminate obtained by the production method of the present invention can also be used for producing a new laminate by laminating with a laminate object in the shape of a film or sheet made of a material other than metal. .. Examples of the object to be laminated include a heat-resistant resin film or sheet, a fiber-reinforced resin sheet, a prepreg, and the like.
A prepreg is preferable as the object to be laminated. Examples of the prepreg include a reinforcing fiber sheet impregnated with a matrix resin.

Examples of the reinforcing fiber sheet include a sheet composed of the reinforcing fibers.
The matrix resin may be a thermoplastic resin or a thermosetting resin. The present invention is particularly effective when a thermoplastic resin having a melting point of 280 ° C. or lower or a thermosetting resin having a thermosetting temperature of 280 ° C. or lower is used as the matrix resin from the viewpoint of low-temperature bonding.
As the matrix resin, one type may be used alone, or two or more types may be used in combination. Further, the matrix resin may contain the filler described in [089] of International Publication No. 2016/017801, or may contain the above-mentioned reinforcing fibers. It may also contain reinforcing fibers and fillers at the same time.

When the matrix resin is a thermosetting resin, the same one as the thermosetting resin mentioned in the description of the liquid composition can be mentioned. As the thermosetting resin, an epoxy resin, polyphenylene oxide, polyphenylene ether, and polybutadiene are preferable.
When the matrix resin is a thermoplastic resin, polyester resin (polyethylene terephthalate, etc.), polyolefin resin (polyethylene, etc.), styrene resin (polystyrene, etc.), polycarbonate, polyimide (aromatic polyimide, etc.), polyarylate, polysulfone, Polyallyl sulfone (polyether sulfone, etc.), aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, polyphenylene ether, PTFE, TFE / PAVE copolymer, TFE / Examples thereof include HFP copolymers and fluororesins such as PCTFE (excluding the polymer (X)).

The temperature of the hot press of the film or laminate obtained by the production method of the present invention and the prepreg is preferably equal to or lower than the melting point of the polymer (X), more preferably 120 to 300 ° C, still more preferably 140 to 240 ° C. 160 to 220 ° C. is more preferable. When the hot press temperature is within the above range, the film or laminate obtained by the production method of the present invention and the prepreg can be attached with excellent adhesion while suppressing thermal deterioration of the prepreg. The resin layer may contain fillers and reinforcing fibers, and the object to be laminated may contain fillers, reinforcing fibers and the polymer (X).
The configuration of the metal laminate including the resin layer and the object to be laminated is not limited to the following, but the metal layer / resin layer / object to be laminated / resin layer / metal layer or metal layer / object to be laminated / resin layer. In the composition of the object to be laminated / the metal layer and the like, the thickness of the resin layer is preferably 0.1 μm to 300 μm, more preferably 0.3 μm to 150 μm, more preferably 0.5 μm to 100 μm, and further preferably 0.7 μm to 70 μm. Preferably, 1 μm to 50 μm is more preferable, and 2 μm to 40 μm is particularly preferable. When it is not more than the upper limit of the above range, the drilling workability as a copper-clad laminate is good and the dielectric property is excellent. If it is at least the lower limit of the above range, the metal layer, the resin layer, and the object to be laminated and the resin layer can be attached with excellent adhesion.

Further, the object to be laminated is a thermoplastic resin, and any one of the thermoplastic resin inner polyimide (aromatic polyimide, etc.), liquid crystal polyester, PTFE, TFE / PAVE copolymer, TFE / HFP copolymer, and PCTFE When 50% by mass or more is contained, or when 50% by mass or more of the above thermoplastic resin is contained in total, the temperature of the hot press between the resin layer and the object to be laminated is preferably 310 to 400 ° C, preferably 320 to 380 ° C. More preferably, 330 to 370 ° C. is further preferable. When the hot press temperature is within the above range, the resin layer and the object to be laminated can be attached with excellent adhesion while suppressing thermal deterioration of the object to be laminated. The resin layer may contain a filler and reinforcing fibers, and the object to be laminated may contain a filler, reinforcing fibers and a copolymer (X).
The configuration of the metal laminate including the resin layer and the object to be laminated is not limited to the following, but the metal layer / resin layer / object to be laminated / resin layer / metal layer or metal layer / object to be laminated / resin layer. In the composition of the object to be laminated / the metal layer and the like, the thickness of the resin layer is preferably 0.1 μm to 300 μm, more preferably 0.3 μm to 150 μm, more preferably 0.5 μm to 100 μm, and further preferably 0.7 μm to 70 μm. Preferably, 1 μm to 50 μm is more preferable, and 2 μm to 40 μm is particularly preferable. When it is not more than the upper limit of the above range, the drilling workability as a copper-clad laminate is good and the dielectric property is excellent. If it is at least the lower limit of the above range, the metal layer, the adhesive layer, and the object to be laminated and the resin layer can be attached with excellent adhesion.
The adhesion (peeling strength) between the film or laminate obtained by the production method of the present invention and the object to be laminated is preferably 5 N / cm or more, more preferably 6 N / cm or more, and particularly preferably 7 N / cm or more.

As the prepreg, a commercially available prepreg can be used.
For example, commercially available prepregs include those having the following trade names.
Panasonic's MEGTRON GX series R-G520, R-1410W, R-1410A, R-1410E, MEGTRON series R-5680, R-5680 (N), R-5670, R-5670 (N), R -5620S, R-5620, R-5630, R-1570, HIPER Series No. R-1650V, R-1650D, R-1650M, R-1650E.
GEA-770G, GEA-705G, GEA-700G, GEA-679FG, GEA-679F (R), GEA-78G, TD-002, GEA-75G, GEA-67, GEA-67G manufactured by Hitachi Kasei Kogyo Co., Ltd.
GEPL-190T, GEPL-230T, GHPL-830X TypeA, GHPL-830NS, GHPL-830NSR, GHPL-830NSF manufactured by Mitsubishi Gas Chemical Company.
GEPL-190T, GEPL-230T, GHPL-830X TypeA, GHPL-830NS, GHPL-830NSR, GHPL-830NSF manufactured by DOOSAN CORPORATION.
GUANDONG Shengyi SCI. SP120N, S1151G, S1151GB, S1170G, S1170GB, S1150G, S1150GB, S1140F, S1140FB, S7045G, SP175M, S1190, S1190B, S1170, S0701, S1141KF, S0401KF, S10002 S1000-2B, S1000, S1000B, S1000H, S1000HB, S7136H, S7439, S7439B.
NY1135, NY1140, NY1150, NY1170, NY2150, NY2170, NY9135, NY9140, NY9600, NY9250, NY9140 HF, NY6200, NY6150, NY3170 LK, NY6300 , NY2170H, NY2170, NY2150, NY2140, NY1600, NY1140, NY9815HF, NY9810HF, NY9815, NY9810.
IT-180GN, IT-180I, IT-180A, IT-189, IT-180, IT-258GA3, IT-158, IT-150GN, IT-140, IT-150GS, IT-150G, IT manufactured by ITEQ CORPORATION -168G1, IT-168G2, IT-170G, IT-170GRA1, IT-958G, IT-200LK, IT-200D, IT-150DA, IT-170GLE, IT-968G, IT-968G SE, IT-968, IT- 968 SE.
UV BLOCK FR-4-86, NP-140 TL / B, NP-140M TL / B, NP-150 R / TL / B, NP-170 R / TL / B, NP-180 R / manufactured by NANYA PLASTICS. TL / B, NPG R / TL / B, NPG-151, NPG-150N, NPG-150LKHD, NPG-170N, NPG-170 R / TL / B, NPG-171, NPG-170D R / TL / B, NPG -180ID / B, NPG-180IF / B, NPG-180IN / B, NPG-180INBK / B (BP), NPG-186, NPG-200R / TL, NPG-200WT, FR-4-86 PY, FR-140TL PY, NPG-PY R / TL, CEM-3-92, CEM-3-92PY, CEM-3-98, CEM-3-01PY, CEM-3-01HC, CEM-3-09, CEM-3-09HT , CEM-3-10, NP-LDII, NP-LDIII, NP-175R / TL / B, NP-155F R / TL / B, NP-175F R / TL / B, NP-175F BH, NP-175FM BH ..
ULVP series and LDP series manufactured by TAIWAN UNION TECHNOLOGY.
A11, R406N, P25N, TERAGreen, I-Tera MT40, IS680 AG, IS680, Astra MT77, G200, DE104, FR408, ED130UV, FR406, IS410, FR402, FR406N, IS420, IS620i, 370TU I-Speed, FR-408HR, IS415, 370HR.
NY9000, NX9000, NL9000, NH9000, N9000-13 RF, N8000Q, N8000, N7000-1, N7000-2 HT Slash-3, N7000-3, N5000, N5000-30, N-5000-32, manufactured by PARK ELECTROCHEMICAL. N4000-12, N4000-12SI, N4000-13, N4000-13SI, N4000-13SI, N4000-13EP, N4000-13EP SI, N4350-13RF, N4380-13RF, N4800-20, N4800-20SI, Meteorwave1000, Meteorwave2000 , Meteorwave4000, Mercurywave9350, N4000-6, N4000-6FC, N4000-7, N4000-7SI, N4000-11, N4000-29.
ROGERS CORPORATION RO4450B, RO4450F, CLITE-P, 3001 Bonding Film, 2929 Bondpley, CuClad 6700 Bonding Film, ULTRALAM 3908 Bondpley, CuClad 6250 Bond.
ES-3329, ES-3317B, ES-3346, ES-3308S, ES-3310A, ES-3306S, ES-3350, ES-3352, ES-3660, ES-3351S, ES-3551S, ES manufactured by Risho Kogyo Co., Ltd. -3382S, ES-3940, ES-3960V, ES-3960C, ES-37353, ES-3305, ES-3615, ES-3306S, ES-3506S, ES-3308S, ES-3317B, ES-3615.

A metal laminate whose metal layer is made of copper, a copper alloy, or the like, which is obtained by using the film produced by the method for producing a film of the present invention or the laminate produced by the method for producing a laminate of the present invention, is printed. It can be used in the manufacture of substrates. A laminate whose base material is made of copper, a copper alloy, or the like, which is produced by the method for producing a laminate of the present invention, can also be used for producing a printed circuit board.
The printed circuit board can be obtained by etching a metal layer such as the metal laminate to form a pattern circuit. A known method can be adopted for etching the metal layer.
In the production of a printed circuit board, a metal layer may be etched to form a pattern circuit, an interlayer insulating film may be formed on the pattern circuit, and a pattern circuit may be further formed on the interlayer insulating film. The interlayer insulating film can be formed, for example, by the liquid composition obtained by the production method of the present invention.
Specifically, for example, the following method can be mentioned. After etching the metal layer of a metal laminate having an arbitrary laminated structure to form a pattern circuit, the liquid composition of the present invention is applied onto the pattern circuit, dried, and then heated to form an interlayer insulating film. Next, a metal layer is formed on the interlayer insulating film by thin film deposition or the like, and etching is performed to form a further pattern circuit.

In the production of the printed circuit board, a solder resist may be laminated on the pattern circuit. The solder resist can be formed, for example, by the liquid composition of the present invention. Specifically, the liquid composition of the present invention may be applied onto a pattern circuit, dried, and then heated to form a solder resist.

Further, in the production of the printed circuit board, the coverlay film may be laminated. The coverlay film is typically composed of a base film and an adhesive layer formed on the surface thereof, and the surface on the adhesive layer side is bonded to the printed circuit board. As the coverlay film, for example, a film obtained by the production method of the present invention can be used.
Further, an interlayer insulating film using the film obtained by the production method of the present invention is formed on a pattern circuit formed by etching a metal layer of a metal laminated plate, and a polyimide film is formed as a coverlay film on the interlayer insulating film. May be laminated.

The obtained printed circuit boards are useful as substrates for electronic devices such as radars, network routers, backplanes, and wireless infrastructures that require high-frequency characteristics, substrates for various sensors for automobiles, and substrates for engine management sensors, and are particularly useful in millimeters. It is suitable for applications aimed at reducing transmission loss in the wave band.

The film or laminate obtained by the manufacturing method of the present invention can be used as an antenna part, a printed circuit board, an aircraft part, an automobile part, a sports equipment, a food industry product, a saw, a covering article such as a sliding bearing, and the like. Further, for example, it can also be used for the uses described in [0040] to [0044] of International Publication No. 2015/182702. Further, the prepreg can be used for FRP and CFRP, and this includes the uses described in [0046] of International Publication No. 2015/182702. The liquid composition of the present invention can also be used as a solution-based coating material. Examples of the article coated with the paint include those described in [0045] of International Publication No. 2015/182702. Further, as in Japanese Patent No. 2686148, it can also be used as an insulating coating material for forming an insulating layer of an insulated electric wire.

Examples of the insulated wire include an insulated wire in which the liquid composition of the present invention is used to form an insulating coating layer having a thickness of 10 to 150 μm on the outer circumference of a flat wire. The relative permittivity of the insulating coating layer is preferably 2.8 or less. Further, it is preferable that the adhesion strength between the insulating coating layer and the metal type used for the flat wire is 10 N / cm or more. The insulated wire is suitable as any device of an insulating amplifier, an isolation transformer, an alternator of an automobile, and an electric motor of a hybrid vehicle.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description. In the following examples, the liquid medium containing the solid particles including the liquid composition of the present invention is referred to as "dispersion liquid".
[Measuring method]
Various measuring methods for the polymer (X) and the resin powder are shown below.
(1) Copolymerization Composition The proportion (mol%) of the unit based on NAH in the copolymerization composition of the polymer (X) was determined by the following infrared absorption spectrum analysis. The proportions of the other units were determined by melt NMR analysis and fluorine content analysis.

<Percentage of units based on NAH (mol%)>
The fluorine-containing copolymer was press-molded to obtain a film having a thickness of 200 μm, which was then analyzed by infrared spectroscopy to obtain an infrared absorption spectrum. In the infrared absorption spectrum, the absorption peak in the NAH-based unit in the fluorine-containing copolymer appears at ^{1778 cm -1.} The absorbance of the absorption peak was measured, and the molar extinction coefficient of NAH 20810 mol ^-1 · l · cm ^-1 was used to determine the proportion of units based on NAH in the fluorine-containing copolymer.

(2) Melting point (° C)
Using a differential scanning calorimeter (DSC device) manufactured by Seiko Electronics Co., Ltd., the melting peak when the temperature of the copolymer (X) is raised at a rate of 10 ° C./min is recorded, and the temperature (° C.) corresponding to the maximum value is recorded. Was defined as the melting point (Tm).

(3) MFR (g / 10 minutes)
Using a melt indexer manufactured by Techno Seven, measure the mass (g) of the copolymer (X) flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm in 10 minutes (unit time) under a load of 49 N at 372 ° C. And made it MFR.

(4) Relative permittivity Dielectric breakdown in a test environment in which the temperature was kept within the range of 23 ° C ± 2 ° C and the relative humidity was kept within the range of 50% ± 5% RH by the transformer bridge method based on ASTM D 150. The relative permittivity was defined as a value obtained at 1 MHz using a test device (YSY-243-100RHO (manufactured by Yamayo Testing Machine Co., Ltd.)).

(5) Average particle size of the polymer (X) 2,000 mesh sieve (opening 2.400 mm), 1.410 mesh sieve (opening 1.705 mm), 1.000 mesh sieve (opening 1.205 mm) , 0.710 mesh sieve (opening 0.855 mm), 0.500 mesh sieve (opening 0.605 mm), 0.250 mesh sieve (opening 0.375 mm), 0.149 mesh sieve (opening 0. 100 mm) and the saucer were stacked in this order from the top. A sample (polymer (X)) was put therein and sieved with a shaker for 30 minutes. After that, the mass of the sample remaining on each sieve was measured, the cumulative mass of passing mass for each opening value was shown in a graph, and the particle size when the cumulative mass of passing mass was 50% was taken as the average particle size of the sample. ..

(6) Average particle size of resin powder and D90
Using a laser diffraction / scattering particle size distribution measuring device (LA-920 measuring device) manufactured by Horiba Seisakusho, the resin powder was dispersed in water, the particle size distribution was measured, and the average particle size (μm) and D90 (μm) were measured. Calculated.

(7) Sparsely Filled Bulk Density and Densely Filled Bulk Density The sparsely filled bulk density and densely packed bulk density of the resin powder were measured by using the methods described in [0117] and [0118] of International Publication No. 2016/017801. ..

(8) Peeling Strength from Copper Foil A rectangular test piece having a length of 100 mm and a width of 10 mm was cut out from the single-sided copper-clad laminate, double-sided copper-clad laminate or laminate obtained in each example. From one end of the test piece in the length direction to a position of 50 mm, one copper foil and the resin layer, and for the test piece not using the copper foil, the resin layer and the mating material fused to each other were peeled off. Next, using a tensile tester (manufactured by Orientec Co., Ltd.), the test piece is peeled 90 degrees at a tensile speed of 50 mm / min with the position 50 mm from one end in the length direction as the center, and the maximum load is set to the peel strength (peeling strength (manufactured by Orientec). N / 10 mm). The larger the peel strength, the better the adhesion between the resin layer and the copper foil or between the resin layer and the mating material.

(9) Warpage rate of single-sided copper-clad laminate A 180 mm square test piece was cut out from the single-sided copper-clad laminate obtained in each example. The warpage rate of this test piece was measured according to the measuring method specified in JIS C 6471. The smaller the warpage rate, the higher the flatness of the printed circuit board, in which when a single-sided copper-clad laminate is laminated with other materials, poor lamination with other materials due to warpage during laminating processing and warpage as a laminated body are suppressed. It becomes possible to obtain.

(10) Thickness direction linear expansion coefficient (ppm / ° C)
The linear expansion coefficient CTE (z) in the thickness direction was measured using a thermomechanical analyzer (TMA402 F1 Hyperion manufactured by NETZSCH) for a sample obtained by cutting the double-sided copper-clad laminate obtained in each example into 10 mm × 10 mm. Specifically, in a nitrogen atmosphere, the load is 19.6 mN, the sample is heated at a rate of 2 ° C./min in the temperature range of -65 ° C to 150 ° C, and the displacement of the sample thickness is measured. bottom. After the measurement was completed, the coefficient of linear expansion from −40 ° C. to 125 ° C. was determined from the displacement of the sample between −40 ° C. and 125 ° C.

(11) Arithmetic Mean Roughness Ra
Based on JIS B0601: 2013 (ISO4287: 1997, Amd.1: 2009), Ra on the surface of the resin layer of the single-sided copper-clad laminate was measured. The reference length rl (cutoff value λc) for the roughness curve when calculating Ra was set to 0.8 mm.

(12) Peeling Strength at Interface with Prepreg A rectangular test piece having a length of 100 mm and a width of 10 mm was cut out from the metal laminated plate obtained in each example. The resin layer and the prepreg were peeled off from one end in the length direction of the test piece to a position of 50 mm. Next, using a tensile tester (manufactured by Orientec Co., Ltd.), the test piece is peeled 90 degrees at a tensile speed of 50 mm / min with the position 50 mm from one end in the length direction as the center, and the maximum load is set to the peel strength (peeling strength (manufactured by Orientec). N / 10 mm). The larger the peel strength, the better the adhesion between the resin layer and the prepreg.

[Manufacturing Example 1]
Unit (1) monomer as NAH (himic anhydride, manufactured by Hitachi Chemical Co., Ltd.) to form an _{a, PPVE (CF 2 = CFO (} CF 2) 3 F, manufactured by Asahi Glass Co., Ltd.) using, WO 2016 / The polymer (X-1) was produced by the procedure described in [0123] of No. 017801.
The copolymer composition of the polymer (X-1) was NAH unit / TFE unit / PPVE unit = 0.1 / 97.9 / 2.0 (mol%). The melting point of the polymer (X-1) was 300 ° C., the relative permittivity was 2.1, the MFR was 17.6 g / 10 minutes, and the average particle size was 1554 μm.

Next, using a jet mill (single track jet mill FS-4 type manufactured by Seishin Enterprise Co., Ltd.), the polymer (X-1) was pulverized under the conditions of a pulverization pressure of 0.5 MPa and a processing speed of 1 kg / hr to form a resin powder. (A) was obtained. The average particle size of the resin powder (A) was 2.58 μm, and the D90 was 7.1 μm. The sparsely packed bulk density of the resin powder (A) was 0.278 g / mL, and the densely packed bulk density was 0.328 g / mL.

[Manufacturing Example 2]
A resin made of PTFE by crushing PTFE (L169J manufactured by Asahi Glass Co., Ltd.) under the conditions of a crushing pressure of 0.5 MPa and a processing speed of 1 kg / hr using a jet mill (single track jet mill FS-4 type manufactured by Seishin Enterprise Co., Ltd.). Powder (B) was obtained. The average particle size of the resin powder (B) was 3.01 μm, D90 was 8.5 μm, the sparsely packed bulk density was 0.355 g / mL, and the densely packed bulk density was 0.387 g / mL. ..

[Example 1]
To 120 g of resin powder (A), a mixed aqueous solution of 9 g of a nonionic surfactant (manufactured by Neos, Futergent 250) and 234 g of distilled water was gradually added, and a stirrer, Labo Stirrer (manufactured by Yamato Kagaku Co., Ltd.). A dispersion (C-1) was obtained by stirring for 60 minutes using Model: LT-500).

[Example 2]
A dispersion liquid (C-2) was obtained in the same manner as in Example 1 except that the nonionic surfactant was changed to FTX-218P (manufactured by Neos) and the distilled water was changed to N-methyl-2-pyrrolidone. rice field.

[Example 3]
A dispersion (C-3) was obtained in the same manner as in Example 1 except that the nonionic surfactant was changed to FTX-218P (manufactured by Neos) and the distilled water was changed to N, N-dimethylformamide. ..

[Example 4]
A dispersion (C-4) was obtained in the same manner as in Example 1 except that the nonionic surfactant was changed to Futagent 710FM (manufactured by Neos) and the distilled water was changed to N, N-dimethylacetamide. ..

[Comparative Example 1]
A dispersion liquid (C-5) was obtained in the same manner as in Example 1 except that the resin powder (B) obtained in Production Example 2 was used instead of the resin powder (A).

[Dispersibility evaluation]
With respect to the dispersions obtained in each example, the dispersion state after standing for 1 hour and after standing for 3 days was visually confirmed, and the dispersibility was evaluated according to the following evaluation criteria.
<After standing for 1 hour>
◯: The resin powder did not settle, and no separation between the resin powder and the liquid medium was observed.
X: The resin powder settles, and separation between the resin powder and the liquid medium is observed.
<After standing for 3 days>
◯: Separation of the resin powder and the liquid medium was observed, but when the mixture was stirred again with a lab stirrer for 6 hours, no floating of agglomerates was observed and redispersion was possible.
X: Separation of the resin powder and the liquid medium was observed, and even if the mixture was stirred again with a lab stirrer for 6 hours, agglomerates were observed to float and could not be redispersed.

The evaluation results of each example are shown in Table 1. The abbreviations in Table 1 have the following meanings.
F250: Futergent 250 (manufactured by Neos)
FTX-218P: FTX-218P (manufactured by Neos)
NMP: N-methyl-2-pyrrolidone DMF: N, N-dimethylformamide DMAc: N, N-dimethylacetamide

As shown in Table 1, the dispersions of Examples 1 to 4 in which the resin powder (A) was dispersed in a liquid medium had a good dispersion state after standing for 1 hour and were excellent in dispersibility. In addition, the resin powder and the liquid medium are separated after standing for 3 days, but when the mixture is stirred again with a lab stirrer for 6 hours, the agglomerates do not float and can be redispersed, which is excellent in redispersibility. rice field.
On the other hand, in the dispersion liquid of Comparative Example 1 in which the resin powder (B) was used instead of the resin powder (A), a part of the resin powder (B) settled and separated from the liquid medium after standing for 1 hour. The dispersion was bad. In addition, after standing for 3 days, all the resin powder (B) settled and separated, and even if the mixture was stirred again with a lab stirrer for 6 hours, the agglomerates floated and a uniform dispersion could not be obtained. The dispersibility was also poor.

[Example 5]
The dispersion liquid (C-1) obtained in Example 1 was applied onto a copper foil and dried to prepare two single-sided copper-clad laminates. Next, two single-sided copper-clad laminates were laminated so that the resin layers faced each other, and vacuum heat pressing was performed at a press temperature of 340 ° C., a press pressure of 4.0 MPa, and a press time of 15 minutes to obtain a double-sided copper-clad laminate. Table 2 shows the measurement results of the relative permittivity and the peel strength after etching the obtained double-sided copper-clad laminate.

[Example 6]
A silica filler (SFP-30M, manufactured by Denka) having an average particle size of 0.7 μm was added to the dispersion liquid (C-2) obtained in Example 2 so as to have a concentration of 25% by mass, and the mixed liquid was added to the dispersion liquid (SFP-30M, manufactured by Denka Co., Ltd.). A double-sided copper-clad laminate was obtained in the same manner as in Example 5 except that it was used in place of C-1). Table 2 shows the measurement results of the peel strength.

[Comparative Example 2]
A double-sided copper-clad laminate was obtained in the same manner as in Example 5 except that the dispersion liquid (C-5) obtained in Comparative Example 1 was used instead of the dispersion liquid (C-1). Table 2 shows the measurement results of the peel strength.

As shown in Table 2, in Examples 5 and 6 using the dispersion liquid of the present invention, the resin in the double-sided copper-clad laminate was compared with Comparative Example 2 using the dispersion liquid (C-1) having a poor dispersion state. The peel strength between the layer and the copper foil was high.

[Example 7]
A dispersion was obtained in the same manner as in Example 1 except that the nonionic surfactant was changed to Futagent 710-FM (manufactured by Neos) and the distilled water was changed to diethylene glycol dibutyl ether. Subsequently, the dispersion liquid obtained as described above was dispersed with a zirconia ball having a diameter of 15 mm using a horizontal ball mill to obtain a dispersion liquid (C-6). A dispersion liquid (C-6) is applied onto a copper foil, dried in a nitrogen atmosphere at 220 ° C. for 15 minutes, then heated at 350 ° C. for 15 minutes, and then slowly cooled to obtain a single-sided copper having a resin layer thickness of 30 μm. Two tension laminates were produced. Next, two single-sided copper-clad laminates were laminated so that the resin layers faced each other, and vacuum heat pressing was performed at a press temperature of 340 ° C., a press pressure of 4.0 MPa, and a press time of 15 minutes to obtain a double-sided copper-clad laminate.

[Example 8]
A dispersion (C-7) was obtained in the same manner as in Example 7 except that diethylene glycol dibutyl ether was changed to butyl carbitol acetate. The dispersion liquid (C-7) was applied onto a copper foil and dried at 250 ° C. for 15 minutes in a nitrogen atmosphere to obtain a single-sided copper-clad laminate and a double-sided copper-clad laminate in the same manner as in Example 7. The warpage rate of the single-sided copper-clad laminate was 4.4%, and the warp was small.

[Example 9]
A dispersion liquid (C-8) was obtained in the same manner as in Example 7 except that butyl carbitol acetate was changed to butyl carbitol. The dispersion liquid (C-8) was applied onto a copper foil and dried at 230 ° C. for 15 minutes in a nitrogen atmosphere to obtain a single-sided copper-clad laminate and a double-sided copper-clad laminate in the same manner as in Example 7. The warpage rate of the single-sided copper-clad laminate was 5.0%, and the warp was small.

[Example 10]
A mixed aqueous solution of 9 g of a nonionic surfactant (Futergent 250, manufactured by Neos) and 234 g of distilled water is gradually added to 120 g of a silica filler (SFP-30M, manufactured by Denka) having an average particle size of 0.7 μm. Then, a dispersion liquid (C-9) was obtained by stirring for 60 minutes using a lab stirrer (manufactured by Yamato Scientific Co., Ltd., model: LT-500). The dispersion liquid (C-1) and the dispersion liquid (C-9) prepared in Example 1 are mixed at a mass ratio of (C-1) :( C-9) = 70:30, and stirred with a lab stirrer. A uniform dispersion was obtained. Subsequently, the dispersion liquid obtained as described above was dispersed with a zirconia ball having a diameter of 15 mm using a horizontal ball mill to obtain a dispersion liquid (C-10). A single-sided copper-clad laminate is prepared by applying a dispersion liquid (C-10) on a copper foil, drying it in a nitrogen atmosphere at 100 ° C. for 15 minutes, heating it at 350 ° C. for 15 minutes, and then slowly cooling it. bottom. The laminated body obtained by molding the obtained laminated body into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 11]
A single-sided copper-clad laminate was produced in the same manner as in Example 10 except that the dispersion liquid (C-11) was obtained by setting (C-1): (C-9) of Example 10 as a mass ratio of 60:40. .. The laminated body obtained by molding the obtained single-sided copper-clad laminate into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 12]
A single-sided copper-clad laminate was produced in the same manner as in Example 10 except that the dispersion liquid (C-12) was obtained by setting (C-1): (C-9) of Example 10 as a mass ratio of 50:50. .. The laminated body obtained by molding the obtained single-sided copper-clad laminate into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 13]
A single-sided copper-clad laminate was produced in the same manner as in Example 10 except that the dispersion liquid (C-13) was obtained by setting (C-1): (C-9) of Example 10 as a mass ratio of 40:60. .. The laminated body obtained by molding the obtained single-sided copper-clad laminate into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 14]
A dispersion (C-14) was obtained in the same manner as in Example 7 except that butyl carbitol acetate was changed to DMF. The dispersion liquid (C-14) is applied onto a copper foil, dried in a nitrogen atmosphere at 150 ° C. for 15 minutes, and then heated at 350 ° C. for 15 minutes to obtain a double-sided copper-clad laminate as in Example 7. rice field.

[Example 15]
A dispersion liquid (C-15) was obtained in the same manner as in Example 7 except that butyl carbitol acetate was changed to DMAC. The dispersion liquid (C-15) was applied onto a copper foil and dried at 165 ° C. for 15 minutes in a nitrogen atmosphere to obtain a double-sided copper-clad laminate in the same manner as in Example 7.

Table 3 shows the peel strength of Examples 7 to 15 and the relative permittivity of Examples 10 to 13.

[Example 16]
The dispersion liquid (C-1) and AD-911E (average particle size 0.25 μm) manufactured by Asahi Glass Co., Ltd., which is a PTFE dispersion liquid, are mixed at a mass ratio of (C-1): AD-911E at a mass ratio of 60:40, and a laboratory is used. The mixture was stirred with a stirrer to obtain a uniform dispersion liquid (D-1). The dispersion liquid (D-1) is applied onto a copper foil, dried in a nitrogen atmosphere at 100 ° C. for 15 minutes, then heated at 350 ° C. for 15 minutes, and then slowly cooled to obtain two single-sided copper-clad laminates. Made. Next, two single-sided copper-clad laminates were laminated so that the resin layers faced each other, and vacuum heat pressing was performed at a press temperature of 340 ° C., a press pressure of 4.0 MPa, and a press time of 15 minutes to obtain a double-sided copper-clad laminate.

[Example 17]
A single-sided copper-clad laminate was prepared by applying the dispersion liquid (C-1) on a copper foil, drying it in a nitrogen atmosphere at 100 ° C. for 15 minutes, heating it at 350 ° C. for 15 minutes, and then slowly cooling it. .. Next, two single-sided copper-clad laminates were stacked around a 0.1 mm-thick PTFE sheet (PTFE sheet manufactured by Yodogawa Hu-Tech Co., Ltd.) so that the resin layers face each other, and the press temperature was 340 ° C., the press pressure was 4.0 MPa, and the press was performed. Vacuum heat pressing was performed for 15 minutes to obtain a double-sided copper-clad laminate.

[Example 18]
A single-sided copper-clad laminate was prepared by applying the dispersion liquid (C-1) on a copper foil, drying it in a nitrogen atmosphere at 100 ° C. for 15 minutes, heating it at 350 ° C. for 15 minutes, and then slowly cooling it. ..
The resin layer of the single-sided copper-clad laminate was laminated so as to be in contact with the polyimide film (manufactured by Toray DuPont, Kapton 100EN; hereinafter also referred to as "PI"), and the press temperature was 340 ° C, the press pressure was 4.0 MPa, and the press time was 15 minutes. A single-sided copper-clad laminate having a copper foil / resin layer / PI structure was produced by vacuum heat pressing. The laminated body obtained by molding the obtained single-sided copper-clad laminate into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 19]
The dispersion liquid (C-1) is applied onto the PI, dried in a nitrogen atmosphere at 100 ° C. for 15 minutes, then heated at 350 ° C. for 15 minutes, and then slowly cooled to form a laminated body having a PI / resin layer structure. Two sheets were prepared. The obtained laminates were laminated so that the resin layers faced each other, and vacuum heat pressing was performed at a press temperature of 340 ° C., a press pressure of 4.0 MPa, and a press time of 15 minutes to prepare a laminate having a PI / resin layer / PI structure. The laminated body obtained by molding the obtained laminated body into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 20]
A single-sided copper-clad laminate was prepared by applying the dispersion liquid (C-1) on a copper foil, drying it in a nitrogen atmosphere at 100 ° C. for 15 minutes, heating it at 350 ° C. for 15 minutes, and then slowly cooling it. ..
The resin layer of the single-sided copper-clad laminate is laminated so as to be in contact with PI, and vacuum heat press is performed at a press temperature of 340 ° C., a press pressure of 4.0 MPa, and a press time of 15 minutes to perform a copper foil / resin layer / PI / resin layer / copper. A double-sided copper-clad laminate with a foil structure was produced.

[Example 21]
The dispersion liquid (C-1) was impregnated into a glass cloth (manufactured by Arisawa Mfg. Co., Ltd., product number: # 1031) and dried at 110 ° C. for 20 minutes to obtain a prepreg. Copper foils were laminated on both sides of the prepreg, and vacuum heat pressing was performed at a press temperature of 340 ° C., a press pressure of 4.0 MPa, and a press time of 15 minutes to prepare a double-sided copper-clad laminate having a copper foil / prepreg / copper foil structure. When the coefficient of linear expansion CTE (z) was measured using the obtained laminated board, it was 189 ppm / ° C.

[Example 22]
The dispersion liquid (C-1) is applied onto a copper foil, dried in a nitrogen atmosphere at 100 ° C. for 15 minutes, then heated at 350 ° C. for 15 minutes, and then slowly cooled to form two single-sided copper-clad laminates. Made. The resin layer of the single-sided copper-clad laminate was laminated so as to be in contact with the epoxy-based prepreg (manufactured by Hitachi Kasei Co., Ltd., GEA-67N), and vacuum heat pressing was performed at a pressing temperature of 180 ° C., a pressing pressure of 3.0 MPa, and a pressing time of 60 minutes. A double-sided copper-clad laminate having a copper foil / resin layer / cured epoxy resin layer / resin layer / copper foil structure was produced.

Table 4 shows the resin layer thickness and peel strength of Examples 16 to 22.

[Example 23]
The single-sided copper-clad laminate obtained in Example 5 was etched to remove the copper foil to obtain a film. The coefficient of thermal expansion in the MD direction (coating direction at the time of dispersion liquid coating) and the TD direction (vertical direction in the MD direction) of the obtained film was measured by a TMA device. As the measuring device, TMA402F1 Hyperion manufactured by NETZSCH is used, the measurement mode is the tensile mode, the measurement temperature is 30 ° C to 100 ° C, the measurement load is 19.6 mN, the temperature rise rate is 5 ° C / min, and the measurement atmosphere is a nitrogen atmosphere. The measurement was carried out below, and the thermal expansion rate when the temperature changed from 30 ° C. to 100 ° C. was measured. The film obtained by molding the obtained film into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 24]
The single-sided copper-clad laminate obtained in Example 14 was etched to remove the copper foil to obtain a film coated with the copper foil. The obtained film was measured for thermal expansion coefficient in the MD direction and the TD direction using a TMA device. The film obtained by molding the obtained film into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Example 25]
The single-sided copper-clad laminate obtained in Example 7 was etched to remove the copper foil to obtain a film coated with the copper foil. The obtained film The obtained film was measured for the coefficient of thermal expansion in the MD direction and the TD direction using a TMA device. The film obtained by molding the obtained film into a 7 cm square did not curl into a cylindrical shape, and warpage was suppressed.

[Comparative Example 3]
A fluororesin film was prepared by a conventionally known method using a commercially available PFA fluororesin. The obtained film of the obtained fluororesin film was measured for the coefficient of thermal expansion in the MD direction and the TD direction using a TMA device. The film obtained by molding the obtained film into a 7 cm square did not curl around once in a cylindrical shape, but warpage was observed.

The coefficients of thermal expansion in the MD direction and the TD direction of Examples 23 to 25 and Comparative Example 3 were determined. The coefficient of thermal expansion is indicated by "+" and the coefficient of contraction is indicated by "-". Table 5 shows each coefficient of thermal expansion (shrinkage rate) in the MD direction / TD direction, the coefficient of thermal expansion (shrinkage) rate, the thickness of the resin layer, and the peel strength.
The coefficient of change in thermal expansion (contraction) is the ratio between the x direction (large coefficient of thermal expansion (contraction)) and the y direction (small coefficient of thermal expansion (contraction)), and is represented by "x / y".

[Example 26]
The double-sided copper-clad laminate obtained in Example 21 was vacuum-heat pressed at a press temperature of 170 ° C. and a press pressure of 0.005 MPa for 30 minutes to perform annealing. The coefficient of linear expansion CTE (z) was measured using the obtained double-sided copper-clad laminate and found to be 45 ppm / ° C.

[Example 27]
To 120 g of the resin powder (A), 12 g of a nonionic surfactant (Futergent 710FL manufactured by Neos) and 234 g of methyl ethyl ketone were put into a horizontal ball mill pot, dispersed with a zirconia ball having a diameter of 15 mm, and a dispersion liquid (a dispersion liquid (A)). C-16) was obtained. The dispersion liquid (C-16) is applied onto a copper foil having a thickness of 12 μm, dried at 100 ° C. for 15 minutes in a nitrogen atmosphere, heated at 350 ° C. for 15 minutes, and then slowly cooled to form a resin layer having a thickness of 7 μm. A single-sided copper-clad laminate having was obtained.
The surface of the resin layer of the obtained single-sided copper-clad laminate was plasma-treated. As the plasma processing apparatus, AP-1000 manufactured by NORDSON MARCH was used. As plasma processing conditions, the RF output of AP-1000 is 300 W, the gap between electrodes is 2 inches, the type of introduced gas is argon (Ar), the introduced gas flow rate is 50 cm ³ / min, the pressure is 13 Pa, and the processing time is 1 minute. And said. The arithmetic mean roughness Ra of the surface of the resin layer after the plasma treatment was 2.5 μm.
FR-4 (manufactured by Hitachi Kasei Co., Ltd., reinforcing fiber: glass fiber, matrix resin: epoxy resin, product name: CEA-67N) on the resin layer side of the single-sided copper foil laminated plate within 72 hours after the surface treatment was performed. 0.2t (HAN), thickness: 0.2mm) were layered, and vacuum heat pressing was performed under the conditions of a press temperature of 185 ° C., a press pressure of 3.0 MPa, and a press time of 60 minutes to obtain a metal laminated plate (No. 1). ).

A single-sided copper-clad laminate was produced in the same manner as above except that the plasma treatment conditions were changed as shown in Table 6, and a metal laminate was obtained in the same manner as above except that the single-sided copper-clad laminate was used (). No. 2-7).

Table 6 shows the plasma treatment conditions of each example, and the measurement results of the arithmetic mean roughness Ra of the surface of the resin layer after the plasma treatment, the surface functional group density, and the peel strength between the resin layer and the layer composed of the prepreg.

As shown in Table 6, No. 1 having a Ra on the surface of the resin layer of 2.0 μm or more. In Nos. 1 to 4, the peel strength between the resin layer and the layer made of the prepreg was high, and their adhesion was excellent.

[Example 28]
The dispersion liquid (C-6) was applied onto a copper foil and dried at 100 ° C. for 15 minutes in a nitrogen atmosphere. The copper foil side of the obtained laminate was attached to a polyimide roll, which is a transport roll of "Noritake Company Limited R to R type NORITAKE far-infrared N2 atmosphere furnace", at a set temperature of 340 ° C. and an oxygen concentration of 200 ppm. It was heated to produce a single-sided copper-clad laminate. The roll speed was adjusted so that the heating time was 1 minute (using a 4.7 m heating furnace, the roll speed was 4.7 m / min).
After the heat treatment, the molten state of the polymer (X) was visually evaluated (No. 1).
The evaluation was visually judged from the number of foreign substances (optically non-uniform substances) remaining after melting and the state of melting. The judgment criteria are shown below.
Number of foreign objects:
The number of foreign substances that can be visually confirmed in the area of 1:10 cm ² is 50 or more and the number of foreign substances that can be visually confirmed in ^{the area of 2:10 cm 2} is 20 to 50 or less 3:10 cm ² area The number of foreign substances that can be visually confirmed in the inside is 20 or less.
1: Some white undissolved residue is seen 2: No white undissolved residue, but partially glossy 3: No undissolved residue (the entire surface looks glossy)

A single-sided copper-clad laminate was manufactured in the same manner as above except that the set temperature (heating temperature), heating time (heating furnace staying time), heating furnace length, and roll speed of each example were changed as shown in Table 7. (No. 2-8).

In addition, No. For 3, 4 and 6, the size of the foreign matter was measured using a microscope. The size of the foreign matter was measured at short and long points from the image taken with a microscope, and the average length of those was taken as the size of the foreign matter. Foreign matter was observed and measured using a SCOPEMAN DIGITAL CCD MICROSCOPE MS-804 manufactured by MORITEX CORPORATION. Foreign substances having a size of more than 30 μm were counted as foreign substances, and foreign substances existing in an area of 10 cm2 were counted. No. In all of 3, 4, and 6, the number of foreign substances that can be confirmed with a microscope in an area of ^{10 cm 2 was 20 or less.}

The films, fiber reinforced films, prepregs, metal laminates, printed circuit boards, etc. obtained in the present invention include antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry supplies, saws, sliding bearings, etc. It can be used as a covering article or the like.
Japanese patent application 2016-144722 filed on July 22, 2016, Japanese patent application 2017-0236385 filed on February 15, 2017, and Japanese patent filed on May 18, 2017. The entire contents of the specification, claims and abstract of application 2017-09294 are cited herein and incorporated as disclosure of the specification of the present invention.

Claims (11)

A resin containing a liquid medium and a resin powder dispersed in the liquid medium, the volume standard cumulative 90% diameter of the resin powder is 8 μm or less, and the resin powder contains the following polymer (X). A liquid composition comprising a powder or an inorganic filler.
Polymer (X): A fluoropolymer having a unit based on tetrafluoroethylene, which has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group. A fluorine-containing polymer having a melting point of 260 to 320 ° C. The liquid composition according to claim 1, wherein the resin powder has an average particle size of 0.3 to 6 μm. The inorganic fillers are silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium hydroxide, magnesium hydroxide, and water. Aluminum oxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, active white clay, sepiolite, imogolite, cericite, glass fiber, glass Claim 1 or 2, which is at least one selected from the group consisting of beads, silica-based balloons, carbon black, carbon nanotubes, carbon nanohorns, graphite, carbon fibers, glass balloons, carbon burns, wood flour and zinc borate. The liquid composition described. The liquid composition according to any one of claims 1 to 3, which comprises the polytetrafluoroethylene powder and the inorganic filler. The liquid composition according to any one of claims 1 to 4, wherein the content of the resin powder is 5 to 500 parts by mass with respect to 100 parts by mass of the polytetrafluoroethylene powder. The invention according to any one of claims 1 to 5, wherein the total content of the polytetrafluoroethylene powder and the inorganic filler is 0.1 to 300 parts by mass with respect to 100 parts by mass of the resin powder. Liquid composition. Claims 1 to 6 wherein the liquid medium is at least one selected from the group consisting of water, alcohols, nitrogen-containing compounds, sulfur-containing compounds, ethers, esters, ketones, glycol ethers and cellosolves. The liquid composition according to any one of the above. The liquid medium is water, γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-pentylketone, methylisobutylketone, Methylisopentyl ketone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene Glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate , Butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, benzene, ethylbenzene, diethylbenzene , Pentylbenzene, isopropylbenzene, toluene, xylene, simene, mesityrene, methanol, ethanol, isopropanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, dimethylformamide, mineral spirit, N, N-dimethylformamide, N, N- Claims 1 to 6, which are at least one selected from the group consisting of dimethylacetamide, N-methyl-2-pyrrolidone, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether and various silicone oils. The liquid composition according to any one of the above. The liquid composition according to any one of claims 1 to 8, wherein the liquid medium is water. The liquid composition according to any one of claims 1 to 9, wherein the liquid composition further contains a nonionic surfactant. A dispersion containing a liquid medium and a resin powder dispersed in the liquid medium, the volume standard cumulative 90% diameter of the resin powder is 8 μm or less, and the resin powder is a resin containing the following polymer (X). A liquid composition obtained by mixing a liquid with polytetrafluoroethylene or an inorganic filler to obtain a liquid composition containing the resin powder, the liquid medium, the polytetrafluoroethylene powder, or the inorganic filler. How to make things.
Polymer (X): A fluoropolymer having a unit based on tetrafluoroethylene, which has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group. A fluorine-containing polymer having a melting point of 260 to 320 ° C.